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Olefination with Sulfonyl Halides and Esters: Synthesis of Unsaturated Sulfonyl Fluorides
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Cite this: Org. Lett. 2022, 24, 23, 4270–4274
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https://doi.org/10.1021/acs.orglett.2c01604
Published June 2, 2022

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Abstract

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Methanedisulfonyl fluoride, CH2(SO2F)2, transforms aromatic aldehydes into β-arylethenesulfonyl fluorides, useful substrates for the SuFEx “click”-type transformations. The reaction mimics mechanism of the Horner–Wadsworth–Emmons olefination, which runs via addition of the carbanion, followed by cyclization–fragmentation of the four-membered ring intermediate. In the absence of base, electron-rich aldehydes follow an alternative pathway of the Knoevenagel condensation to provide unsaturated 1,1-disulfonyl fluorides. We demonstrate also trapping of elusive ethene-1,1-disulfonyl fluoride, CH2═C(SO2F)2, with 4-(dimethylamino)pyridine (DMAP) that forms zwitterionic adduct, characterized with X-ray studies.

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Sulfur Fluoride Exchange reaction (SuFEx) is a valuable tool for “click”-type formation of the S–O, S–N, and S–C bonds, applied in organic synthesis, drug-discovery, molecular biology, and material science. (1,2) Unique substrates for the transformations are sulfonyl fluorides, which display unprecedented combination of stability and reactivity. (3) The contradictory features of the reagents inspired the term ‘sleeping beauties’, which, apparently intact, awake on demand to react in the most desired way. (2) Among them β-arylethenesulfonyl fluorides, ArCH═CHSO2F, are recognized as selectively addressable bis-electrophiles, able to react as Michael acceptors, or via sulfur substitution, depending on the reaction conditions. (4) Historical methods of their preparation consist of chlorosulfonation–fluorination of styrenes, (5) and Horner–Wadsworth–Emmons olefination of arylaldehydes, followed by scission of intermediate sulfonate, chlorination, and halogen exchange. (6) More efficient, one-step procedures developed recently by Qin, Sharpless, Arvidsson, and others, utilize Heck–Matsuda couplings of ethenesulfonyl fluoride, CH2═CHSO2F (ESF), (7) with arenediazonium salts, (4) aryl boronates, (8) and iodoarenes. (9) In the follow-up studies, similar approach was demonstrated also for the C–H alkenylation of arenes, in processes directed by functional groups, (10) or governed by π-electron distribution of the aromatic substrates. (11) Only recently, mechanistically distinct radical fluorosulfonation of alkenes with SO2ClF under blue LED irradiation was developed by Liao (Scheme 1, top). (12)

Scheme 1

Scheme 1. Literature Methods of Synthesis of β-Arylethenesulfonyl Fluorides (Top), and Selected Pentacoordinated Sulfur(VI) Systems (Bottom)
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Our research group explores organic transformations of sulfonyl- and carbonyl-containing substrates, demonstrated on functionalization of nitroarenes, (13) synthesis and transformations of sulfonyl fluorides, (14) and carbonyl olefination reactions. (15) Recently, we developed olefination with sulfonyl halides and esters, which mimics the Horner-Wadsworth-Emmons reaction of alkanephosphonates. (16) Accordingly, sulfonyl-stabilized carbanions add to the carbonyl groups of aldehydes or ketones, and so-formed aldol-type adducts cyclize to four-membered ring intermediates, which fragment to alkenes. Although the reaction was reported for the first time in 1990 by Hawkins, (17) and in 1991 by Kagabu, (18) the preliminary results remained practically unknown in the chemical literature. Inspiration of the Hawkins’ pioneered studies was a report on tricyclic sulfurane I, synthesized by Martin (Scheme 1, bottom). (19) The pentacoordinated, trigonal bipyramidal sulfur atom present in the structure was stabilized by chelation with electronegative hexafluoroalkoxide ligands, whereas more donating analogues underwent rapid degenerate rearrangement between tetracoordinated sulfonates. (20) Later, unchelated SO2X3(−) anions bearing strongly electron-withdrawing ligands (X = F and CF3) were reported as moderately stable species (II (21) and III, (22) respectively), and postulated as intermediates in deoxyfluorination of phenols via aryl fluorosulfonates (IV). (23) Importantly, similar structural motif can be recognized in transient four-membered ring intermediates of the sulfonyl-based olefination (V). Indeed, observations of Hawkins (17) and us (15a,b) fully confirmed that only sulfonates of fluorinated alcohols and phenols are able to give alkenes, whereas nonactivated neopentyl esters fail to undergo second step of the reaction (only initial aldol-type adducts are formed). In turn more electrophilic sulfonyl fluorides were reported as precursors for the synthesis of stilbenes and cinnamyl-type products; (18) e.g., Kagabu demonstrated that ethyl fluorosulfonylacetate, FSO2CH2CO2Et, reacts with benzaldehyde in the presence of NEt3 to afford ethyl cinnamate, isolated in 78% yield. (18b) Based on this precedent we reckoned that methanedisulfonyl fluoride, CH2(SO2F)2 (MDSF, 1), may act as a symmetrical precursor, in which one of the SO2F groups reacts in the olefination process, (24) and the latter remains installed on the newly formed C═C bond. In our report we present direct, one-step transformation of arylaldehydes into β-arylethenesulfonyl fluorides, and spontaneous Knoevenagel-type condensation of 1 with electron-rich aldehydes.

Our studies began from the preparation of methanedisulfonyl fluoride (1) in two steps, starting from inexpensive acetic acid, POCl3, and HSO3Cl, (25) and followed by double halogen exchange (SO2Cl → SO2F) with KHF2 in dry acetonitrile. (26) After short optimization the synthesis was carried out on a 1 mol scale, and 1 was isolated by distillation in 67% yield over two steps. (27) Attempts at model reaction of 1 with 2-naphthaldehyde started from conditions described by Kagabu. (18b) We observed that the process runs rather slowly, thus requires prolonged heating in boiling THF, and displays strong effect of structure of the amine base on the reaction course. After testing 11 low molecular weight tertiary amines, we selected N-methylpyrrolidine, as a reagent of choice, able to yield the expected 2-(2-naphthyl)ethenesulfonyl fluoride (2u, 70%), as an exclusive E-isomer. (27) Results of reactions with other aldehydes are presented in Scheme 2.

Scheme 2

Scheme 2. Synthesis of β-Arylethenesulfonyl Fluorides in the Reaction of 1 with Arylaldehydes
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aThe reaction carried out with 1,2,2,6,6-pentamethylpiperidine, as a base, gave 17% of 2l.

bThe reaction carried out at rt gave 25% of 2p, accompanied by byproduct.

Surprisingly, the scope and limitation studies revealed a rather disappointing observation that the highest yields of 2 are obtained for arylaldehydes with neutral substitution pattern, whereas presence of donors and acceptors decreases product yields. Origins of the effect were partially revealed, when pure samples of isolated sulfonyl fluorides, bearing naphthyl (2u) and 4-trifluoromethylphenyl group (2t), were subjected to standard olefination conditions. In the first case most of the product remained intact and was recovered in 95%, whereas more electrophilic CF3-substituted sulfonyl fluoride partially decomposed and was recovered in only 42%. Accordingly, prolonged heating of the products with amine may cause slow degradation, likely due to Michael-type addition and polymerization events.

Additionally, a useful hint regarding cause of lower yields obtained for electron-rich substrates was given from reaction of 4-methylsalicylaldehyde, which unexpectedly led to sulfocoumarin, substituted with the SO2F group (3a, 29%). The reaction mimicked process described recently by Yang for ethyl chlorosulfonyl acetate, ClSO2CH2CO2Et, in which analogous sulfocoumarin-3-carboxylates were formed in good yields. (28) On the basis of the reported procedure and our own experimentation, (27) we chose pyridine in 1,2-dichloroethane (DCE) at 65 °C as optimal conditions and performed a few reactions with salicylaldehydes (Scheme 3).

Scheme 3

Scheme 3. Synthesis of Sulfocoumarins in the Reaction of 1 with Salicylaldehydes
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aThe reaction carried out under olefination conditions (cf. Scheme 2) gave 29% of 3a.

bThe reaction with salicylaldehyde was carried out for 7 d. Similar de(fluorosulfonylation) process was observed for 3-methyl- and 5-methylsalicylaldehydes.

cAnalytical sample of 3d was isolated in 33% of yield.

dAnalytical sample of 3d′ was isolated in 6% of yield.

7-Methyl- (3a), naphthyl- (3b), and 7-methoxysulfocoumarin (3c) were isolated in 58–67% yield, and structure of the latter was confirmed with X-ray studies. Importantly, 6- and 7-alkoxysubstituted sulfocoumarins are potent and selective inhibitors of human carbonic anhydrases (hCA); (29) thus, their methods of preparation are in great demand. Unfortunately, under these conditions, parent salicylaldehyde and its 3- and 5-methyl derivatives formed hardly separable mixtures of products, resulted from partial removal of the fluorosulfonyl group. Interestingly, similar removal of the ester function was demonstrated on sulfocoumarin-3-carboxylates under Happer’s decarboxylation conditions (LiI, DMF, reflux). (28) Mechanism of formation of the sulfocoumarins, proposed by Yang, consisted of initial generation of sulfene, which adds to the phenoxide, and so-formed aryl sulfonate cyclizes by condensation with the carbonyl group. (28) However, we supposed that for MDSF (1) the order of events is plausibly reversed: namely, carbonyl group of the aldehyde condenses to the Knoevenagel-type adduct, and then one of the fluorosulfonyl groups is forced toward substitution with proximal phenoxide anion. The idea has been supported by isolation of condensation product with donor-substituted 4-(dimethylamino)benzaldehyde, when the olefination was attempted at rt (4n, 39%). (27) Interestingly, the same reaction was already reported in 1979 by Yagupolskii et al., who heated the substrates in acetic anhydride at 50 °C for 3 h (yield 84%). (30) Based on this, we reasoned that under olefination conditions more electron-rich aldehydes form styrenes bearing two fluorosulfonyl groups, which likely decompose in the presence of amine at higher temperature. Similar obstacles were considered by Qin et al. in studies of condensation of halomethanesulfonyl fluorides, HalCH2SO2F, with cinnamaldehydes, promoted by pyrrolidine. (31) Yet further support, based on literature data, arose from report on condensation of cinnamaldehydes with close analog of 1: bis(trifluoromethanesulfonyl)methane, CH2(SO2CF3)2. Yanai et al. reported that the condensation runs spontaneously in DCE at rt for 3–10 h, giving crystalline, yellowish-colored products, stable on air, (32) and the process is promoted by the substrate, which is strong Brønsted acid. Surprisingly, our literature search revealed that both CH2(SO2CF3)2 and 1 display essentially the same acidity in DMSO (pKa = 2.4), (33) being stronger than, e.g., trifluoroacetic acid (pKa = 3.45). (32a) Based on this we attempted synthesis of the Knoevenagel-type adducts with electron-rich aldehydes. To facilitate separation of the expected products we applied conditions of Yanai, but concentrated DCM solutions of substrates were additionally layered with hexane and left at rt overnight. After slow diffusional mixing of the organic phases, we observed formation of yellowish, millimeter-size block crystals of cinnamaldehyde derivative 4a, isolated in two crops in 85% yield, and characterized with X-ray studies. Analogously, set of products 4b–o was obtained in excellent yields, as shown at Scheme 4. (27)

Scheme 4

Scheme 4. Synthesis of Unsaturated 1,1-Disulfonyl Fluorides via Knoevenagel Condensation of 1 with Electron-Rich Aldehydes
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aProduct 4n was reported in the literature. (30)

bNo precipitate was formed.

Interestingly, when donor properties of benzaldehyde substituents decreased in the series from 4-Me2N, to 2,4-diMeO, and to 4-MeO, yields of the condensation products also decreased from 94% for 4n, to 42% for 4o, and to only 10% of conversion, observed by 1H NMR (Scheme 4, bottom). (27) The trend was consistent with observations by Yanai, who isolated benzaldehyde adduct with CH2(SO2CF3)2 in only 7% yield, and earlier report by Zhu, (34) who forced dehydration reaction with acetic anhydride, but after isolation observed fast decomposition to substrates. The facts taken together lead to the rather unusual conclusion that formation of the condensation products is thermodynamically controlled with electronic (push–pull) stabilization between π-electron system and bissulfonyl center, and thus counterintuitively more electrophilic aldehydes give lower yields of 4, than electron-rich ones.

Following our inspiration with reactivity of the CH2(SO2CF3)2, we considered generation of condensation product of 1 with formaldehyde. As ethenesulfonyl fluoride (ESF) (7) is considered to be the most prefect Michael acceptor ever found, (35) one would expect that analogue bearing two fluorosulfonyl groups may supersede its electrophilic properties and become another useful hub for the SuFEx processes. (2,3b) On the basis of literature data we heated 1 with paraformaldehyde and substituted pyridines in DCE. (32b) Although 2-fluoropyridine, pyridine, and 2-fluoro-4-(dimethylamino)pyridine gave complex mixtures of products, reaction with nucleophilic 4-(dimethylamino)pyridine (DMAP) led to the formation of white precipitate 5, isolated in 81% yield (Scheme 5, top). (27)

Scheme 5

Scheme 5. Follow-up Studies: Generation of Transient Ethene-1,1-disulfonyl Fluoride, and X-ray Structure of Its Zwitterionic Adduct with DMAP, 5
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aThe bond lengths were taken from X-ray structures of compounds 3c, 4a, 4o, and 5, averaged for each molecule, and given in Å. Hydrogen atoms were omitted for clarity.

Structure of 5, established with X-ray studies, revealed a unique zwitterionic form, which paralleled structures of related bis(trifluoromethanesulfonyl) derivatives, reported in the literature. (32b,36) Stabilization of negative charge with two SO2F groups caused planarization of the carbanionic center and resulted in alternations of the C–S (−0.07 Å) and S–F (+0.03 Å) bond lengths, as compared with neutral structures of 3c, 4a, and 4o (Scheme 5, bottom). To the best of our knowledge, 5 represents one of the very few examples of stable carbanions of sulfonyl fluorides, (37) which usually eliminate to sulfenes.

In conclusion, we presented one-step transformation of arylaldehydes into β-arylethenesulfonyl fluorides, using easily accessible methanedisulfonyl fluoride (1). With electron-rich aldehydes (e.g., cinnamaldehydes) the precursor spontaneously condenses, to afford Knoevenagel-type products, isolated in excellent yields. Transient ethene-1,1-bissulfonyl fluoride, formed in reaction of 1 with paraformaldehyde in the presence of DMAP, gives stable zwitterionic adduct, with planar carbanionic center, stabilized with two SO2F groups. The presented results expand armory of synthetic methods for preparation of valuable SuFEx reagents, and understanding of their activation and reactivity.

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CCDC 2161680–2161683 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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Author Information

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  • Corresponding Author
  • Authors
    • Michał Tryniszewski - Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland
    • Dariusz Basiak - Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work was financed by the OPUS 16 program (Grant No. DEC-2018/31/B/ST5/01118) of the National Science Centre, Poland.

References

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This article references 37 other publications.

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    A series of vinyl sulfonate esters, vinyl sulfonamides, and vinyl sulfones I (R = OEt, OPh, NHMe, NHCH2Ph, NHCH2CH2Ph, NHPh, Ph, CH2Ph, CH2CH2Ph; R1 = CH2CH2Ph, Me) was prepd. as an effort to develop potent and selective cruzain inhibitors. Alkyl vinyl sulfonamides, e.g. I (R = NHCH2Ph, R1 = Me), were relatively weak inhibitors of cruzain, while aryl vinyl sulfonamides and sulfonate esters, e.g. I (R = OEt, OPh, NHPh; R1 = Me, CH2CH2Ph) were much more potent.
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  7. 7
    Meng, Y.-P.; Wang, S.-M.; Fang, W.-Y.; Xie, Z.-Z.; Leng, J.; Alsulami, H.; Qin, H.-L. Ethenesulfonyl Fluoride (ESF) and Its Derivatives in SuFEx Click Chemistry and More. Synthesis 2020, 52, 673– 687,  DOI: 10.1055/s-0039-1690038
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    7
    Ethenesulfonyl Fluoride (ESF) and Its Derivatives in SuFEx Click Chemistry and More
    Meng, Yan-Ping; Wang, Shi-Meng; Fang, Wan-Yin; Xie, Zhi-Zhong; Leng, Jing; Alsulami, Hamed; Qin, Hua-Li
    Synthesis (2020), 52 (5), 673-687CODEN: SYNTBF; ISSN:1437-210X. (Georg Thieme Verlag)
    A review. This review summarizes the chem. properties and applications of ethenesulfonyl fluoride in click chem., org. chem., materials science, medicinal chem. and in many other fields related to org. synthesis.
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  8. 8
    Chinthakindi, P. K.; Govender, K. B.; Sanjeeva Kumar, A.; Kruger, H. G.; Govender, T.; Naicker, T.; Arvidsson, P. I. A Synthesis of “Dual Warhead” β-Aryl Ethenesulfonyl Fluorides and One-Pot Reaction to β-Sultams. Org. Lett. 2017, 19, 480– 483,  DOI: 10.1021/acs.orglett.6b03634
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    8
    A Synthesis of "Dual Warhead" β-Aryl Ethenesulfonyl Fluorides and One-Pot Reaction to β-Sultams
    Chinthakindi, Praveen K.; Govender, Kimberleigh B.; Kumar, A. Sanjeeva; Kruger, Hendrik G.; Govender, Thavendran; Naicker, Tricia; Arvidsson, Per I.
    Organic Letters (2017), 19 (3), 480-483CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
    Herein, we report an operationally simple, ligand- and additive-free oxidative boron-Heck coupling that is compatible with the ethenesulfonyl fluoride functional group. The protocol proceeds at room temp. with chemoselectivity and E-isomer selectivity and offers facile access to a wide range of β-aryl/heteroaryl ethenesulfonyl fluorides from com. boronic acids. Furthermore, we demonstrate a "one-pot click" reaction to directly transform the products to aryl-substituted β-sultams.
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  9. 9
    Zha, G.-F.; Zheng, Q.; Leng, J.; Wu, P.; Qin, H.-L.; Sharpless, K. B. Palladium-Catalyzed Fluorosulfonylvinylation of Organic Iodides. Angew. Chem., Int. Ed. 2017, 56, 4849– 4852,  DOI: 10.1002/anie.201701162
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    9
    Palladium-Catalyzed Fluorosulfonylvinylation of Organic Iodides
    Zha, Gao-Feng; Zheng, Qinheng; Leng, Jing; Wu, Peng; Qin, Hua-Li; Sharpless, K. Barry
    Angewandte Chemie, International Edition (2017), 56 (17), 4849-4852CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    In the presence of Pd(OAc)2, ethenesulfonyl fluoride underwent chemo-, regio- and diastereoselective aerobic Heck reactions with aryl, heteroaryl, and vinyl iodides mediated by silver trifluoroacetate in acetone to yield arylvinylsulfonyl fluorides such as (E)-PhCH:CHSO2F and (E,E)-PhCH:CHCH:CHSO2F in 24-99% yields. The structure of (E,E)-PhCH:CHCH:CHSO2F was detd. by x-ray crystallog.
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  10. 10
    Li, C.; Wang, S.-M.; Qin, H.-L. A Rh-Catalyzed Air and Moisture Tolerable Aldehyde (Ketone)-Directed Fluorosulfonylvinylation of Aryl C(sp2)-H Bonds. Org. Lett. 2018, 20, 4699– 4703,  DOI: 10.1021/acs.orglett.8b02037
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    10
    A Rh-Catalyzed Air and Moisture Tolerable Aldehyde (Ketone)-Directed Fluorosulfonylvinylation of Aryl C(sp2)-H Bonds
    Li, Chen; Wang, Shi-Meng; Qin, Hua-Li
    Organic Letters (2018), 20 (15), 4699-4703CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
    The first Rh-catalyzed activation of ortho sp2 C-H bonds of aldehydes (ketones) for monoselective coupling with ethenesulfonyl fluoride was accomplished without covalent or transient preinstallation of imines. The 42 examples revealed that the developed method has the advantage of a wide scope and functional-group tolerability. Application of this method for complicated natural product modification was also accomplished.
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  11. 11
    Chen, X.-Y.; Wu, Y.; Zhou, J.; Wang, P.; Yu, J.-Q. Synthesis of β-Arylethenesulfonyl Fluoride via Pd-Catalyzed Nondirected C–H Alkenylation. Org. Lett. 2019, 21, 1426– 1429,  DOI: 10.1021/acs.orglett.9b00165
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    11
    Synthesis of β-Arylethenesulfonyl Fluoride via Pd-Catalyzed Nondirected C-H Alkenylation
    Chen, Xiao-Yue; Wu, Yichen; Zhou, Jian; Wang, Peng; Yu, Jin-Quan
    Organic Letters (2019), 21 (5), 1426-1429CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
    (E)-β-Arylvinylsulfonyl fluorides were prepd. by chemoselective and diastereoselective nondirected alkenylation of arenes (as limiting reagents) with ethenesulfonyl fluoride in the presence of Pd(OAc)2 and 5-(pentafluoroethyl)-3-trifluoromethyl-2-pyridinol with AgOAc as stoichiometric oxidant in either hexafluoroisopropanol or CHCl3. The method was used for late-stage functionalization of pharmaceutical compds. and in selected case, the arylvinylsulfonyl fluorides were functionalized.
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  12. 12
    Nie, X.; Xu, T.; Song, J.; Devaraj, A.; Zhang, B.; Chen, Y.; Liao, S. Radical Fluorosulfonylation: Accessing Alkenyl Sulfonyl Fluorides from Alkenes. Angew. Chem., Int. Ed. 2021, 60, 3956– 3960,  DOI: 10.1002/anie.202012229
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    12
    Radical Fluorosulfonylation: Accessing Alkenyl Sulfonyl Fluorides from Alkenes
    Nie, Xingliang; Xu, Tianxiao; Song, Jinshuai; Devaraj, Anandkumar; Zhang, Bolun; Chen, Yong; Liao, Saihu
    Angewandte Chemie, International Edition (2021), 60 (8), 3956-3960CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Sulfonyl fluorides have widespread applications in many fields. In particular, their unique biol. activity has drawn considerable research interest in the context of chem. biol. and drug discovery in the past years. Therefore, new and efficient methods for the synthesis of sulfonyl fluorides are highly in demand. In contrast to extensive studies on FSO2+-type reagents, a radical fluorosulfonylation reaction with a fluorosulfonyl radical (FSO2.) remains elusive so far, probably owing to its instability and difficulty in generation. Herein, the development of the first radical fluorosulfonylation of alkenes based on FSO2 radicals generated under photoredox conditions is reported. This radical approach provides a new and general access to alkenyl sulfonyl fluorides, including structures that would otherwise be challenging to synthesize with previously established cross-coupling methods. Moreover, extension to the late-stage fluorosulfonylation of natural products is also demonstrated.
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  13. 13
    (a) Antoniak, D.; Barbasiewicz, M. Corey-Chaykovsky Cyclopropanation of Nitronaphthalenes: Access to Benzonorcaradienes and Related Systems. Org. Lett. 2019, 21, 9320– 9325,  DOI: 10.1021/acs.orglett.9b03375
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    13a
    Corey-Chaykovsky Cyclopropanation of Nitronaphthalenes: Access to Benzonorcaradienes and Related Systems
    Antoniak, Damian; Barbasiewicz, Michal
    Organic Letters (2019), 21 (23), 9320-9325CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
    Nitronaphthalene derivs. react as Michael acceptors in the Corey-Chaykovsky reaction with alkyl Ph selenones and alkyl di-Ph sulfonium salts. Mechanistic studies reveal that sterically demanding substituents at the carbanionic center favor formation of cyclopropanes and suppress competitive β-elimination to the alkylated products. The transformation, demonstrated also on heterocyclic nitroquinoline and nitroindazolines, is an example of transition metal-free dearomatization method.
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    (b) Antoniak, D.; Barbasiewicz, M. Alkylation of Nitropyridines via Vicarious Nucleophilic Substitution. Org. Lett. 2022, 24, 516– 519,  DOI: 10.1021/acs.orglett.1c03920
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    13b
    Alkylation of Nitropyridines via Vicarious Nucleophilic Substitution
    Antoniak, Damian; Barbasiewicz, Michal
    Organic Letters (2022), 24 (2), 516-519CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
    Electrophilic nitropyridines reacted with sulfonyl-stabilized carbanions gave alkylated nitropyridins I [R = H, Me, n-octyl, etc.; R1 = Me, Et, n-octyl, etc.; R2 = H, OMe, SPh, etc.] products of C-H alkylation via vicarious nucleophilic substitution was reported. The process consisted of formation of the Meisenheimer-type adduct, followed by base-induced β-elimination of the sulfinic acid (e.g., PhSO2H).
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  14. 14
    (a) Talko, A.; Barbasiewicz, M. Nucleophilic Fluorination with Aqueous Bifluoride Solution: Effect of the Phase-Transfer Catalyst. ACS Sustainable Chem. Eng. 2018, 6, 6693– 6701,  DOI: 10.1021/acssuschemeng.8b00489
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    14a
    Nucleophilic Fluorination with Aqueous Bifluoride Solution: Effect of the Phase-Transfer Catalyst
    Talko, Alicja; Barbasiewicz, Michal
    ACS Sustainable Chemistry & Engineering (2018), 6 (5), 6693-6701CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
    Nucleophilic fluorination of sulfonyl chlorides, acyl chlorides, and alkyl sulfonates with satd. aq. soln. of potassium bifluoride (KHF2) was studied under liq.-liq. two-phase conditions. Original "on-water" procedure, reported by Sharpless et al., was tested on model 1-octanesulfonyl chloride in the presence of phase transfer catalysts, some of which appeared to be beneficial for the reaction rate. Despite the high hydration energy of the fluoride ions, the catalytic system displayed numerous features typical for interfacial transportation of the nucleophilic species, being controlled by amt. and structure of the catalyst, lipophilicity of the catalyst's counterion, and rate of stirring. Besides for synthesis of acyl fluorides presence of 1 mol % of tetrabutylammonium chloride affected the selectivity of the reaction by minimizing formation of carboxylic acids and anhydrides. The presented results suggest that aq. solns. of bifluorides (or synthetically equiv. systems accessible by acidification of alkali metal fluoride solns.) can be efficient sources of the fluoride ions under two-phase conditions, provided that rate of the intrinsic reaction is sufficiently high. The methodol. supplements family of nucleophilic fluorinations, delivering a more reactive form of the solvated anions.
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    (b) Talko, A.; Antoniak, D.; Barbasiewicz, M. Directed ortho-Metalation of Arenesulfonyl Fluorides and Aryl Fluorosulfates. Synthesis 2019, 51, 2278– 2286,  DOI: 10.1055/s-0037-1610877
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    14b
    Directed ortho-Metalation of Arenesulfonyl Fluorides and Aryl Fluorosulfates
    Talko, Alicja; Antoniak, Damian; Barbasiewicz, Michal
    Synthesis (2019), 51 (11), 2278-2286CODEN: SYNTBF; ISSN:1437-210X. (Georg Thieme Verlag)
    Studies on directed ortho-metalation (DoM) of arenesulfonyl fluorides (ArSO2F) with in-situ electrophile trapping were presented. Under optimized conditions (LDA, THF, -78 °), a series of model substrates was mono- and difunctionalized with trimethylsilyl chloride in good yields. The synthetic results reveal powerful directing character of the SO2F group, being ahead of bromine and methoxy substituents. Under the same metalation conditions, aryl fluorosulfates (ArOSO2F) display fragmentation to arynes and migration of the SO2F group to the ortho position (anionic thia-Fries rearrangement).
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  15. 15
    (a) Górski, B.; Talko, A.; Basak, T.; Barbasiewicz, M. Olefination with Sulfonyl Halides and Esters: Scope, Limitations, and Mechanistic Studies of the Hawkins Reaction. Org. Lett. 2017, 19, 1756– 1759,  DOI: 10.1021/acs.orglett.7b00517
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    15a
    Olefination with Sulfonyl Halides and Esters: Scope, Limitations, and Mechanistic Studies of the Hawkins Reaction
    Gorski, Bartosz; Talko, Alicja; Basak, Tymoteusz; Barbasiewicz, Michal
    Organic Letters (2017), 19 (7), 1756-1759CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
    Carbanions of alkanesulfonyl halides and esters, particularly 2,2,2-trifluoroethyl sulfonates, reacted with nonenolizable carbonyl compds. (aryl aldehydes, benzophenone, trans-cinnamaldehyde) to give alkenes. Mechanistic studies reveal that initial aldol-type addn. of the carbanions is followed by cyclization and fragmentation to alkenes; the leaving group on the sulfonyl moiety controls the carbanion stability and thus the rate of olefin formation.
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    (b) Górski, B.; Basiak, D.; Talko, A.; Basak, T.; Mazurek, T.; Barbasiewicz, M. Olefination with Sulfonyl Halides and Esters: E-Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors. Eur. J. Org. Chem. 2018, 2018, 1774– 1784,  DOI: 10.1002/ejoc.201701766
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    15b
    Olefination with Sulfonyl Halides and Esters: E-Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors
    Gorski, Bartosz; Basiak, Dariusz; Talko, Alicja; Basak, Tymoteusz; Mazurek, Tomasz; Barbasiewicz, Michal
    European Journal of Organic Chemistry (2018), 2018 (15), 1774-1784CODEN: EJOCFK; ISSN:1099-0690. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Carbanions of sulfonyl halides and activated sulfonates add to carbonyl compds., and so-formed aldol-type adducts spontaneously fragment into olefins. This transformation mimics the one-pot Julia olefination with (hetero)aryl sulfones, but the mechanism of fragmentation involves a four-membered intermediate, typical for reactivity of phosphorus reagents. Moreover, in contrast to the reactions of sulfones, sulfonates of fluorinated alcs. (TFE and HFI) produce byproducts that are easily removed during workup. In our report, we focus on reactions of unstabilized and semistabilized carbanion precursors: alkylsulfonates, and allyl- and benzylsulfonates, resp. In particular for semistabilized systems, olefins were synthesized as predominant E isomers in good yields. The presented studies reveal that optimal reaction conditions, including the type of base and alc. groups of the sulfonates, are different depending on stabilization of the carbanion precursors and structure of the carbonyl substrates. The practical synthetic guide is supplemented with a discussion of the mechanism, based on reactivity studies of intermediates and identification of side-products.
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    (c) Górski, B.; Basiak, D.; Grzesiński, Ł.; Barbasiewicz, M. Stereodivergent synthesis of alkenes by controllable syn-/anti-fragmentation of β-hydroxysulfonyl intermediates. Org. Biomol. Chem. 2019, 17, 7660– 7663,  DOI: 10.1039/C9OB01563A
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    Stereodivergent synthesis of alkenes by controllable syn-/anti-fragmentation of β-hydroxysulfonyl intermediates
    Gorski, Bartosz; Basiak, Dariusz; Grzesinski, Lukasz; Barbasiewicz, Michal
    Organic & Biomolecular Chemistry (2019), 17 (33), 7660-7663CODEN: OBCRAK; ISSN:1477-0520. (Royal Society of Chemistry)
    The redn. of the carbonyl group in acylated trifluoroethyl alkanesulfonates follows the Felkin-Ahn selectivity, and the so-formed diastereomeric β-hydroxysulfonyl intermediates undergo syn- and anti-fragmentation, depending on the reaction conditions. In effect, isomeric E- and Z-alkenes are formed in a stereodivergent manner, which mimics the mechanistic manifold of the Peterson olefination.
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    (d) Basiak, D.; Barbasiewicz, M. Olefination with sulfonyl halides and esters – sulfur-based variant of the Horner–Wadsworth–Emmons reaction. ARKIVOC 2021, part ii, 118– 135, (a review)
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    Roman, D.; Sauer, M.; Beemelmanns, C. Applications of the Horner-Wadsworth-Emmons Olefination in Modern Natural Product Synthesis. Synthesis 2021, 53, 2713– 2739,  DOI: 10.1055/a-1493-6331
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    Applications of the Horner-Wadsworth-Emmons Olefination in Modern Natural Product Synthesis
    Roman, David; Sauer, Maria; Beemelmanns, Christine
    Synthesis (2021), 53 (16), 2713-2739CODEN: SYNTBF; ISSN:1437-210X. (Georg Thieme Verlag)
    A review. The application of HWE olefinations in total syntheses of structurally different natural products covering 2015 to 2020 was highlighted. Applied HWE reagents and reactions conditions are highlighted to support future synthetic approaches and serve as guideline to find the best HWE conditions for the most complicated natural products.
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    Hawkins, J. M.; Lewis, T. A.; Raw, A. S. Substituent Effects on Sulfonate Ester Based Olefinations. Tetrahedron Lett. 1990, 31, 981– 984,  DOI: 10.1016/S0040-4039(00)94408-3
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    Substituent effects on sulfonate ester based olefinations
    Hawkins, Joel M.; Lewis, Timothy A.; Raw, Andre S.
    Tetrahedron Letters (1990), 31 (7), 981-4CODEN: TELEAY; ISSN:0040-4039.
    Olefination of carbonyl compds. by the anions of sulfonate esters derived from acidic alcs. is reported. The dependence of the yield and stereochem. of olefination on the sulfonate ester's alkoxy substituent are consistent with a mechanism where apicophilic alkoxy groups promote olefination via a 10-S-5 intermediate.
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    (a) Kagabu, S.; Hara, K.; Takahashi, J. Alkene Formation through Condensation of Phenylmethanesulphonyl Fluoride with Carbonyl Compounds. J. Chem. Soc., Chem. Commun. 1991, 408– 410,  DOI: 10.1039/c39910000408
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    Alkene formation through condensation of phenylmethanesulfonyl fluoride with carbonyl compounds
    Kagabu, Shinzo; Hara, Kenji; Takahashi, Junko
    Journal of the Chemical Society, Chemical Communications (1991), (6), 408-10CODEN: JCCCAT; ISSN:0022-4936.
    Arylmethanesulfonyl fluorides RCH2SO2F (R = Ph, 4-ClC6H4, 4-MeC6H4) condense with arom., aliph., and conjugated aldehydes and ketones R1COR2 (R1 = Ph, 4-ClC6H4, 3-O2NC6H4, PhCH2, PhCH:CH, Me2CHCH2, etc., R2 = H; R1 = R2 = Me) in the presence of potassium carbonate and dibenzo-18-crown-6 to give aryl-substituted alkenes RCH:CR1R2 in satisfactory to modest yields.
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    (b) Kagabu, S.; Shimizu, C.; Takahashi, J.; Hara, K.; Koketsu, M.; Ishida, M. Reaction of phenyl- and alkoxycarbonylmethanesulfonyl fluoride with activated haloalkanes. Bull. Soc. Chim. Fr. 1992, 129, 435– 439
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    Reaction of phenyl- and alkoxycarbonylmethanesulfonyl fluoride with activated haloalkanes
    Kagabu, S.; Shimizu, C.; Takahashi, J.; Hara, K.; Koketsu, M.; Ishida, M.
    Bulletin de la Societe Chimique de France (1992), 129 (5), 435-9CODEN: BSCFAS; ISSN:0037-8968.
    Arylmethanesulfonyl fluorides, ArCH2SO2F (Ar = Ph, 4-O2NC6H4, 4-ClC6H4, 4-MeC6H4), condense with BrCH2Y (Y = COPh, COC6H4Br-4, COMe, COCMe3, CO2Et, PhCH:CH, cyano, Ph) by attacking at the methylenyl carbon instead of the carbonyl bond to give ArCH:CHY. FSO2CH2R (I, R = CO2Me, CO2Et, cyano) were prepd. by fluorination of ClSO2CH2R with KF. I (R = CO2Et) reacts with the carbonyl bonds of R1CHO (R1 = Ph, 4-ClC6H4, 2-MeC6H4, α-thienyl, α-naphthyl, CHMe2, etc.) to give R1CH:CHCO2Et, whereas it attacks the phenacyl bromide exclusively at the α-carbon to give PhCOCH:CHCO2Et. The reaction mode of these sulfonyl fluorides is discussed on the basis of kinetic data.
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    Perkins, C. W.; Wilson, S. R.; Martin, J. C. Ground-state analogs of transition states for attack at sulfonyl, sulfinyl, and sulfenyl sulfur: a sulfuranide dioxide (10-S-5) salt, a sulfuranide oxide (10-S-4) salt, and a sulfuranide (10-S-3) salt. J. Am. Chem. Soc. 1985, 107, 3209– 3218, and references cited therein  DOI: 10.1021/ja00297a029
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    19
    Ground-state analogs of transition states for attack at sulfonyl, sulfinyl, and sulfenyl sulfur: a sulfuranide dioxide (10-S-5) salt, a sulfuranide oxide (10-S-4) salt, and a sulfuranide (10-S-3) salt
    Perkins, C. W.; Wilson, S. R.; Martin, J. C.
    Journal of the American Chemical Society (1985), 107 (11), 3209-18CODEN: JACSAT; ISSN:0002-7863.
    The prepn. and properties of anionic 10-S-5 (I), 10-S-4 (II), and 10-S-3 (III) are described. Crystallog. shows that these compds. have pseudotrigonal bipyramidal geometry in the solid state. PKa data and low-temp. NMR also support major contributions of hypervalent bonding to the ground-state structures in soln. I and II are, resp., the first examples of sulfuramide dioxide and sulfuramide oxide anions. The pKa data show that I, II, and III are more stable than their open chain analogs by at least 2.6, 5.9, and 7.5 kcal/mol, resp. The crystallog. of I, II, and III and the implications that the isolation and characterization of these salts have on the mechanisms of associative nucleophilic displacement at S are discussed.
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    A kinetic study of the cyclization of o-RR1C(OH)C6H4SO2NMe2 (R = R1 = H, Me, Et, Me2CH, Ph; R = H, R1 = Me) to sultones (I) in acid soln. showed huge rate accelerations by the gem-dialkyl groups; these accelerations increased with steric bulk. Relief of initial-state strain was the dominant factor governing the intramol. catalysis. The conjugate base of sultone II underwent a rapid degenerate rearrangement rather than conversion to a sym. pentavalent S intermediate of pseudotrigonal bipyramidal geometry. The high rate of the symmetrization reaction further illustrated the accelerating effect of the gem-dialkyl substituents. A convenient prepn. of o-alkenylbenzenesulfonamides was described.
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    Synthesis and characterization of tetramethylammonium trifluorosulfate
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    Chemistry - A European Journal (2011), 17 (3), 925-929CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
    [Me4N]+[SO2F3]-, the 1st example of a [SO2F3]- salt, was prepd. from Me4NF and SO2F2. The colorless, microcryst. solid was characterized by its IR and Raman spectra. The trigonal bipyramidal structure of C2v symmetry of the [SO2F3]- anion is predicted by ab initio calcns. Two O atoms with d(SO) = 143.2 pm and 1 F atom with d(SF) = 157.9 pm occupy the equatorial plane. The 2 F atoms in the axial position with d(SF) = 168.5 pm are repulsed by the 2 O atoms forming a bent axis with ∠(FaxSFax) = 165.2°.
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    Noncyclic [10-S-5] Sulfuranide Dioxide Salts with Three S-C Bonds: A New Class of Stable Hypervalent Compounds
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    Journal of the American Chemical Society (2003), 125 (41), 12366-12367CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Ph triflate reacts with CF3SiMe3/Q+F- (Q+ = [K(18-crown-6)]+, Me4N+) and (Me2N)3S+Me3SiF2- to afford the first noncyclic [10-S-5] sulfuranide dioxide salts, [(CF3)3SO2]-Q+, with three S-C bonds, whose mol. structure was detd. by x-ray crystallog.
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    Journal of the American Chemical Society (2017), 139 (4), 1452-1455CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    This report describes a method for the deoxyfluorination of phenols with sulfuryl fluoride (SO2F2) and tetramethylammonium fluoride (NMe4F) via aryl fluorosulfonate (ArOFs) intermediates. We first demonstrate that the reaction of ArOFs with NMe4F proceeds under mild conditions (often at room temp.) to afford a broad range of electronically diverse and functional group-rich aryl fluoride products. This transformation was then translated to a one-pot conversion of phenols to aryl fluorides using the combination of SO2F2 and NMe4F. Ab initio calcns. suggest that carbon-fluorine bond formation proceeds via a concerted transition state rather than a discrete Meisenheimer intermediate.
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    An alternative mechanism of the olefination may consist of reaction of aldehyde with FO2SCH(−)SO2N(+)R3, formed via elimination of fluoride and addition of N-methylpyrrolidine.

    There is no corresponding record for this reference.
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    RCH(SO2Cl)2 (I; R = H, Cl) were prepd. by the reaction of a RCH2CO2H with ClSO3H. Thus, reaction of 1:2:2 mixts. of RCH2CO2H (R = H, Cl), ClSO3H, and POCl3 at 105-10° gave 75% I (R = H) (II) and 65% I (R = Cl), resp. Reaction of (HO)2P(O)CH2CO2H with ClSO3H and POCl3 at 90° gave 60% ClSO2CH2P(O)Cl2. Chlorination of II with N-chlorosuccinimide and SOCl2 gave 86% Cl2C(SOCl2)2.
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    The reaction of methanedisulfonyl difluoride with an N-halosuccinimide gave dihalomethanedisulfonyl difluorides. The hitherto unknown monohalogenomethanedisulfonyl fluorides can be prepd. by the treatment of potassium or silver bis[(trifluoromethyl)sulfonyl]methanide with chlorine, bromine and iodine. The related fluorine derivs. were obtained by the electrochem. fluorination of methanedisulfonyl fluoride in anhyd. HF. Besides the known difluoromethanedisulfonyl fluoride, fluoromethanedisulfonyl fluoride could be isolated as a byproduct.
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    See the Supporting Information for details.

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    Herein, a simple, one-pot procedure for the synthesis of structurally diverse sulfonocoumarin-3-carboxylates I (R1 = H, 7-OMe, 6-F, etc.) by heating 2-hydroxyaryl aldehydes with an active sulfonyl chlorides in the presence of pyridine is described. The process tolerates numerous functional groups including alkoxy, alkyl, halogen, nitro, and even nucleophilic phenolic hydroxy. Addnl., reactions of 2-hydroxyaryl ketones and 2-methylaminoaryl aldehydes give 4-substituted sulfocoumarins and 1-aza-2-sulfocoumarins, resp. A gram-scale synthesis and further derivatizations are also reported. The ester group is easily removed via Happer's decarboxylation.
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    Treating CH2(SO2Cl)2 with anhyd. ZnF2 or AgF at 100° gave CH2(SO2F)2 (I) in 82 and 57.4% yield, resp. I condensed with p-Me2NC6H4CHO, RC6H4I(OAc)2 (R = H, m-O2N) and Me2SO to give 84% p-Me2NC6H4CH:C(SO2F)2, 89-93% RC6H4I:C(SO2F)2 (same R) and 83% Me2S:C(SO2F)2, resp.
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    Zhang, Zai-Wei; Wang, Shi-Meng; Fang, Wan-Yin; Lekkala, Ravindar; Qin, Hua-Li
    Journal of Organic Chemistry (2020), 85 (21), 13721-13734CODEN: JOCEAH; ISSN:0022-3263. (American Chemical Society)
    A pyrrolidine-mediated Knoevenagel-type reaction for highly stereoselective construction of novel α-halo-1,3-dienylsulfonyl fluorides was achieved in up to 100% Z-selectivity and high yields at room temp. from condensation of the readily available aldehydes and halomethanesulfonyl fluorides. This protocol provided a class of unique α-halo-1,3-dienylsulfonyl fluorides with wide scope and excellent functional group compatibility. The α-halo-1,3-dienylsulfonyl fluorides were used as versatile building blocks in sulfur fluoride exchange click chem., Suzuki reaction, and Sonogashira reaction for the assembly of highly functionalized dienyl sulfonyl fluoride derivs. to be applied as covalent warheads for the discovery of new drugs.
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    Tetrahedron Letters (2013), 54 (17), 2160-2163CODEN: TELEAY; ISSN:0040-4039. (Elsevier Ltd.)
    A convenient and practical synthesis of 1,1-bis(triflyl)alkenes, e.g. I [Ar = Ph, 4-MeC6H4, 2-BrC6H4, etc.; Tf = triflyl] via self-promoting condensation of Tf2CH2 and aldehydes was developed and chem. behavior of these alkenes was investigated. Among the alkenes, easily isolable 1,1-bis(triflyl)alkadienes derived from α,β-unsatd. aldehydes could be used as useful building blocks for 1,1-bis(triflyl)alkanes. The 1,1-bis(triflyl)alkane thus obtained showed catalyst activity in the acetal forming reaction, which is a typical reaction catalyzed by Bronsted acids.
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    2-(Pyridinium-1-yl)-1,1-bis(perfluoroalkylsulfonyl)ethan-1-ide: A Practical Reagent for Synthesis of Strongly Acidic 1,1-Bis(perfluoroalkylsulfonyl)alkanes
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    Chemistry - A European Journal (2017), 23 (34), 8203-8211CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
    On mixing (RfSO2)2CH2 (Rf=perfluoroalkyl), paraformaldehyde, and substituted pyridines, a three-component reaction proceeded smoothly to give unusual zwitterions bearing both pyridinium and stabilized carbanion moieties in good to excellent yields [e.g., Tf2CH2 + (CH2O)n + pyridine → I (quant.)]. Of these, 2-fluoropyridinium derivs. rapidly dissocd. in acetonitrile to give equil. mixts. of the zwitterions and (RfSO2)2C=CH2/2-fluoropyridine, as confirmed by detailed variable-temp. NMR studies. The dynamic behavior of such 2-fluoropyridinium compds. allows them to be used as shelf-stable, easy-to-handle sources of (RfSO2)2C=CH2. With these reagents, strongly acidic carbon acids (RfSO2)2CHR were synthesized, which served as a new type of acid catalysts. Moreover, C-C bond-forming reactions with a ketene silyl acetal proceeded efficiently with Tf2C=CH2 generated in situ.
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    The kinetics of the reactions of ethenesulfonyl fluoride (ESF) with sulfonium and pyridinium ylides were measured photometrically to det. the electrophilicity parameter of ESF according to the correlation lg k20 °C=sN(N+E). With E=-12.09, ESF is among the strongest Michael acceptors in our comprehensive electrophilicity scale, which explains its excellent performance in reactions with many nucleophiles. Its predicted usability as a reagent in electrophilic arom. substitutions with electron-rich arenes was confirmed by uncatalyzed reactions with alkyl-substituted pyrroles.
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    Interaction of 2,4,6-tris(fluorosulfonyl)chlorobenzene with O-, N-, S-, C-nucleophiles and F-anion
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  • Abstract

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    Scheme 1

    Scheme 1. Literature Methods of Synthesis of β-Arylethenesulfonyl Fluorides (Top), and Selected Pentacoordinated Sulfur(VI) Systems (Bottom)
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    Scheme 2

    Scheme 2. Synthesis of β-Arylethenesulfonyl Fluorides in the Reaction of 1 with Arylaldehydes
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    aThe reaction carried out with 1,2,2,6,6-pentamethylpiperidine, as a base, gave 17% of 2l.

    bThe reaction carried out at rt gave 25% of 2p, accompanied by byproduct.

    Scheme 3

    Scheme 3. Synthesis of Sulfocoumarins in the Reaction of 1 with Salicylaldehydes
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    aThe reaction carried out under olefination conditions (cf. Scheme 2) gave 29% of 3a.

    bThe reaction with salicylaldehyde was carried out for 7 d. Similar de(fluorosulfonylation) process was observed for 3-methyl- and 5-methylsalicylaldehydes.

    cAnalytical sample of 3d was isolated in 33% of yield.

    dAnalytical sample of 3d′ was isolated in 6% of yield.

    Scheme 4

    Scheme 4. Synthesis of Unsaturated 1,1-Disulfonyl Fluorides via Knoevenagel Condensation of 1 with Electron-Rich Aldehydes
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    aProduct 4n was reported in the literature. (30)

    bNo precipitate was formed.

    Scheme 5

    Scheme 5. Follow-up Studies: Generation of Transient Ethene-1,1-disulfonyl Fluoride, and X-ray Structure of Its Zwitterionic Adduct with DMAP, 5
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    aThe bond lengths were taken from X-ray structures of compounds 3c, 4a, 4o, and 5, averaged for each molecule, and given in Å. Hydrogen atoms were omitted for clarity.

  • References

    This article references 37 other publications.

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      A review. Aryl sulfonyl chlorides (e.g. Ts-Cl) are beloved of org. chemists as the most commonly used SVI electrophiles, and the parent sulfuryl chloride, O2SVICl2, also was relied on to create sulfates and sulfamides. However, the desired halide substitution event is often defeated by destruction of the sulfur electrophile because the SVI-Cl bond is exceedingly sensitive to reductive collapse yielding SIV species and Cl-. Fortunately, the use of sulfur(VI) fluorides (e.g., R-SO2-F and SO2F2) leaves only the substitution pathway open. As with most of click chem., many essential features of sulfur(VI) fluoride reactivity were discovered long ago in Germany. Surprisingly, this extraordinary work faded from view rather abruptly in the mid-20th century. Here the authors seek to revive it, along with John Hyatt's unnoticed 1979 full paper exposition on CH2=CH-SO2-F, the most perfect Michael acceptor ever found. To this history the authors add several new observations, including that the otherwise very stable gas SO2F2 has excellent reactivity under the right circumstances. Also proton or silicon centers can activate the exchange of S-F bonds for S-O bonds to make functional products, and the sulfate connector is surprisingly stable toward hydrolysis. Applications of this controllable ligation chem. to small mols., polymers, and biomols. are discussed.
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      A review. SuFEx (Sulfur Fluoride Exchange) is a modular, next generation family of click reactions, geared towards the rapid and reliable assembly of functional mols. This review discusses the growing no. of applications of SuFEx, which can be found in nearly all areas of modern chem.; from drug discovery to materials science.
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      A review. The advent of sulfur(VI)-fluoride exchange (SuFEx) processes as transformations with click-like reactivity has invigorated research into electrophilic species featuring a sulfur-fluorine bond. Among these, sulfonyl fluorides have emerged as the workhorse functional group, with diverse applications being reported. Sulfonyl fluorides are used as electrophilic warheads by both medicinal chemists and chem. biologists. The balance of reactivity and stability that is so attractive for these applications, particularly the resistance of sulfonyl fluorides to hydrolysis under physiol. conditions, has provided opportunities for synthetic chemists. New synthetic approaches that start with sulfur-contg. substrates include the activation of sulfonamides using pyrilium salts, the deoxygenation of sulfonic acids, and the electrochem. oxidn. of thiols. Employing non-sulfur-contg. substrates has led to the development of transition-metal-catalyzed processes based on palladium, copper and nickel, as well as the use of SO2F2 gas as an electrophilic hub. Selectively manipulating mols. that already contain a sulfonyl fluoride group has also proved to be a popular tactic, with metal-catalyzed processes again at the fore. Finally, coaxing sulfonyl fluorides to engage with nucleophiles, when required, and under suitable reaction conditions, has led to new activation methods. This Review provides an overview of the challenges in the efficient synthesis and manipulation of these intriguing functional groups.
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      Recent progress in the synthesis of sulfonyl fluorides for SuFEx click chemistry
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      A review. Since the sulfur(VI) fluoride exchange reaction (SuFEx) was introduced by Sharpless and co-workers in 2014, this new-generation click chem. has emerged as an efficient and reliable tool for creating modular intermol. connections. Sulfonyl fluorides, one of the most important sulfur(VI) fluoride species, have attracted enormous attention in diverse fields, ranging from org. synthesis and material science, to chem. biol. and drug discovery. This review aims to introduce seminal and recent progresses on the synthetic methods of sulfonyl fluorides, which include arom., aliph., alkenyl, and alkynyl sulfonyl fluorides. While not meant to be exhaustive, the purpose is to give a timely overview and insight in this field, and stimulate the development of more efficient synthetic methods of sulfonyl fluorides.
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      A review. Sulfonyl fluoride (SF)-contg. substances are currently attracting enormous attention among practitioners of both chem. biol. and synthetic org. chem. The groups of Jones and Liskamp have demonstrated the potential of sulfonyl fluorides as selective covalent inhibitors in studies related to drug discovery and chem. biol., resp., in the last few years. The Sharpless group has extended the repertoire of "click-reactions" to those involving sulfonyl fluorides, i.e., sulfur-fluoride exchange (SuFEx), a development that quickly triggered the interest in this functional group in the community of synthetic org. chemists. In this microreview, we aim to give an account of the synthetic chem. surrounding sulfonyl fluoride contg. substances from a historical perspective to present day developments.
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      Qin, H.-L.; Zheng, Q.; Bare, G. A.L.; Wu, P.; Sharpless, K. B. A Heck–Matsuda Process for the Synthesis of β-Arylethenesulfonyl Fluorides: Selectively Addressable Bis-electrophiles for SuFEx Click Chemistry. Angew. Chem., Int. Ed. 2016, 55, 14155– 14158,  DOI: 10.1002/anie.201608807
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      Some new aromatic ethene sulfonyl chlorides (I) were conveniently prepd. by the reaction of vinyl compds. with sulfuryl chloride in HCONMe2.
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      A series of vinyl sulfonate esters, vinyl sulfonamides, and vinyl sulfones I (R = OEt, OPh, NHMe, NHCH2Ph, NHCH2CH2Ph, NHPh, Ph, CH2Ph, CH2CH2Ph; R1 = CH2CH2Ph, Me) was prepd. as an effort to develop potent and selective cruzain inhibitors. Alkyl vinyl sulfonamides, e.g. I (R = NHCH2Ph, R1 = Me), were relatively weak inhibitors of cruzain, while aryl vinyl sulfonamides and sulfonate esters, e.g. I (R = OEt, OPh, NHPh; R1 = Me, CH2CH2Ph) were much more potent.
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      Meng, Y.-P.; Wang, S.-M.; Fang, W.-Y.; Xie, Z.-Z.; Leng, J.; Alsulami, H.; Qin, H.-L. Ethenesulfonyl Fluoride (ESF) and Its Derivatives in SuFEx Click Chemistry and More. Synthesis 2020, 52, 673– 687,  DOI: 10.1055/s-0039-1690038
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      Ethenesulfonyl Fluoride (ESF) and Its Derivatives in SuFEx Click Chemistry and More
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      A review. This review summarizes the chem. properties and applications of ethenesulfonyl fluoride in click chem., org. chem., materials science, medicinal chem. and in many other fields related to org. synthesis.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitlCjtr%252FK&md5=6d72938164d46be3db59e6af6ed88812
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      Chinthakindi, P. K.; Govender, K. B.; Sanjeeva Kumar, A.; Kruger, H. G.; Govender, T.; Naicker, T.; Arvidsson, P. I. A Synthesis of “Dual Warhead” β-Aryl Ethenesulfonyl Fluorides and One-Pot Reaction to β-Sultams. Org. Lett. 2017, 19, 480– 483,  DOI: 10.1021/acs.orglett.6b03634
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      A Synthesis of "Dual Warhead" β-Aryl Ethenesulfonyl Fluorides and One-Pot Reaction to β-Sultams
      Chinthakindi, Praveen K.; Govender, Kimberleigh B.; Kumar, A. Sanjeeva; Kruger, Hendrik G.; Govender, Thavendran; Naicker, Tricia; Arvidsson, Per I.
      Organic Letters (2017), 19 (3), 480-483CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
      Herein, we report an operationally simple, ligand- and additive-free oxidative boron-Heck coupling that is compatible with the ethenesulfonyl fluoride functional group. The protocol proceeds at room temp. with chemoselectivity and E-isomer selectivity and offers facile access to a wide range of β-aryl/heteroaryl ethenesulfonyl fluorides from com. boronic acids. Furthermore, we demonstrate a "one-pot click" reaction to directly transform the products to aryl-substituted β-sultams.
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      Zha, G.-F.; Zheng, Q.; Leng, J.; Wu, P.; Qin, H.-L.; Sharpless, K. B. Palladium-Catalyzed Fluorosulfonylvinylation of Organic Iodides. Angew. Chem., Int. Ed. 2017, 56, 4849– 4852,  DOI: 10.1002/anie.201701162
      9
      Palladium-Catalyzed Fluorosulfonylvinylation of Organic Iodides
      Zha, Gao-Feng; Zheng, Qinheng; Leng, Jing; Wu, Peng; Qin, Hua-Li; Sharpless, K. Barry
      Angewandte Chemie, International Edition (2017), 56 (17), 4849-4852CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      In the presence of Pd(OAc)2, ethenesulfonyl fluoride underwent chemo-, regio- and diastereoselective aerobic Heck reactions with aryl, heteroaryl, and vinyl iodides mediated by silver trifluoroacetate in acetone to yield arylvinylsulfonyl fluorides such as (E)-PhCH:CHSO2F and (E,E)-PhCH:CHCH:CHSO2F in 24-99% yields. The structure of (E,E)-PhCH:CHCH:CHSO2F was detd. by x-ray crystallog.
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      Li, C.; Wang, S.-M.; Qin, H.-L. A Rh-Catalyzed Air and Moisture Tolerable Aldehyde (Ketone)-Directed Fluorosulfonylvinylation of Aryl C(sp2)-H Bonds. Org. Lett. 2018, 20, 4699– 4703,  DOI: 10.1021/acs.orglett.8b02037
      10
      A Rh-Catalyzed Air and Moisture Tolerable Aldehyde (Ketone)-Directed Fluorosulfonylvinylation of Aryl C(sp2)-H Bonds
      Li, Chen; Wang, Shi-Meng; Qin, Hua-Li
      Organic Letters (2018), 20 (15), 4699-4703CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
      The first Rh-catalyzed activation of ortho sp2 C-H bonds of aldehydes (ketones) for monoselective coupling with ethenesulfonyl fluoride was accomplished without covalent or transient preinstallation of imines. The 42 examples revealed that the developed method has the advantage of a wide scope and functional-group tolerability. Application of this method for complicated natural product modification was also accomplished.
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      Chen, X.-Y.; Wu, Y.; Zhou, J.; Wang, P.; Yu, J.-Q. Synthesis of β-Arylethenesulfonyl Fluoride via Pd-Catalyzed Nondirected C–H Alkenylation. Org. Lett. 2019, 21, 1426– 1429,  DOI: 10.1021/acs.orglett.9b00165
      11
      Synthesis of β-Arylethenesulfonyl Fluoride via Pd-Catalyzed Nondirected C-H Alkenylation
      Chen, Xiao-Yue; Wu, Yichen; Zhou, Jian; Wang, Peng; Yu, Jin-Quan
      Organic Letters (2019), 21 (5), 1426-1429CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
      (E)-β-Arylvinylsulfonyl fluorides were prepd. by chemoselective and diastereoselective nondirected alkenylation of arenes (as limiting reagents) with ethenesulfonyl fluoride in the presence of Pd(OAc)2 and 5-(pentafluoroethyl)-3-trifluoromethyl-2-pyridinol with AgOAc as stoichiometric oxidant in either hexafluoroisopropanol or CHCl3. The method was used for late-stage functionalization of pharmaceutical compds. and in selected case, the arylvinylsulfonyl fluorides were functionalized.
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    12. 12
      Nie, X.; Xu, T.; Song, J.; Devaraj, A.; Zhang, B.; Chen, Y.; Liao, S. Radical Fluorosulfonylation: Accessing Alkenyl Sulfonyl Fluorides from Alkenes. Angew. Chem., Int. Ed. 2021, 60, 3956– 3960,  DOI: 10.1002/anie.202012229
      12
      Radical Fluorosulfonylation: Accessing Alkenyl Sulfonyl Fluorides from Alkenes
      Nie, Xingliang; Xu, Tianxiao; Song, Jinshuai; Devaraj, Anandkumar; Zhang, Bolun; Chen, Yong; Liao, Saihu
      Angewandte Chemie, International Edition (2021), 60 (8), 3956-3960CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Sulfonyl fluorides have widespread applications in many fields. In particular, their unique biol. activity has drawn considerable research interest in the context of chem. biol. and drug discovery in the past years. Therefore, new and efficient methods for the synthesis of sulfonyl fluorides are highly in demand. In contrast to extensive studies on FSO2+-type reagents, a radical fluorosulfonylation reaction with a fluorosulfonyl radical (FSO2.) remains elusive so far, probably owing to its instability and difficulty in generation. Herein, the development of the first radical fluorosulfonylation of alkenes based on FSO2 radicals generated under photoredox conditions is reported. This radical approach provides a new and general access to alkenyl sulfonyl fluorides, including structures that would otherwise be challenging to synthesize with previously established cross-coupling methods. Moreover, extension to the late-stage fluorosulfonylation of natural products is also demonstrated.
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    13. 13
      (a) Antoniak, D.; Barbasiewicz, M. Corey-Chaykovsky Cyclopropanation of Nitronaphthalenes: Access to Benzonorcaradienes and Related Systems. Org. Lett. 2019, 21, 9320– 9325,  DOI: 10.1021/acs.orglett.9b03375
      13a
      Corey-Chaykovsky Cyclopropanation of Nitronaphthalenes: Access to Benzonorcaradienes and Related Systems
      Antoniak, Damian; Barbasiewicz, Michal
      Organic Letters (2019), 21 (23), 9320-9325CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
      Nitronaphthalene derivs. react as Michael acceptors in the Corey-Chaykovsky reaction with alkyl Ph selenones and alkyl di-Ph sulfonium salts. Mechanistic studies reveal that sterically demanding substituents at the carbanionic center favor formation of cyclopropanes and suppress competitive β-elimination to the alkylated products. The transformation, demonstrated also on heterocyclic nitroquinoline and nitroindazolines, is an example of transition metal-free dearomatization method.
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      (b) Antoniak, D.; Barbasiewicz, M. Alkylation of Nitropyridines via Vicarious Nucleophilic Substitution. Org. Lett. 2022, 24, 516– 519,  DOI: 10.1021/acs.orglett.1c03920
      13b
      Alkylation of Nitropyridines via Vicarious Nucleophilic Substitution
      Antoniak, Damian; Barbasiewicz, Michal
      Organic Letters (2022), 24 (2), 516-519CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
      Electrophilic nitropyridines reacted with sulfonyl-stabilized carbanions gave alkylated nitropyridins I [R = H, Me, n-octyl, etc.; R1 = Me, Et, n-octyl, etc.; R2 = H, OMe, SPh, etc.] products of C-H alkylation via vicarious nucleophilic substitution was reported. The process consisted of formation of the Meisenheimer-type adduct, followed by base-induced β-elimination of the sulfinic acid (e.g., PhSO2H).
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    14. 14
      (a) Talko, A.; Barbasiewicz, M. Nucleophilic Fluorination with Aqueous Bifluoride Solution: Effect of the Phase-Transfer Catalyst. ACS Sustainable Chem. Eng. 2018, 6, 6693– 6701,  DOI: 10.1021/acssuschemeng.8b00489
      14a
      Nucleophilic Fluorination with Aqueous Bifluoride Solution: Effect of the Phase-Transfer Catalyst
      Talko, Alicja; Barbasiewicz, Michal
      ACS Sustainable Chemistry & Engineering (2018), 6 (5), 6693-6701CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
      Nucleophilic fluorination of sulfonyl chlorides, acyl chlorides, and alkyl sulfonates with satd. aq. soln. of potassium bifluoride (KHF2) was studied under liq.-liq. two-phase conditions. Original "on-water" procedure, reported by Sharpless et al., was tested on model 1-octanesulfonyl chloride in the presence of phase transfer catalysts, some of which appeared to be beneficial for the reaction rate. Despite the high hydration energy of the fluoride ions, the catalytic system displayed numerous features typical for interfacial transportation of the nucleophilic species, being controlled by amt. and structure of the catalyst, lipophilicity of the catalyst's counterion, and rate of stirring. Besides for synthesis of acyl fluorides presence of 1 mol % of tetrabutylammonium chloride affected the selectivity of the reaction by minimizing formation of carboxylic acids and anhydrides. The presented results suggest that aq. solns. of bifluorides (or synthetically equiv. systems accessible by acidification of alkali metal fluoride solns.) can be efficient sources of the fluoride ions under two-phase conditions, provided that rate of the intrinsic reaction is sufficiently high. The methodol. supplements family of nucleophilic fluorinations, delivering a more reactive form of the solvated anions.
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      (b) Talko, A.; Antoniak, D.; Barbasiewicz, M. Directed ortho-Metalation of Arenesulfonyl Fluorides and Aryl Fluorosulfates. Synthesis 2019, 51, 2278– 2286,  DOI: 10.1055/s-0037-1610877
      14b
      Directed ortho-Metalation of Arenesulfonyl Fluorides and Aryl Fluorosulfates
      Talko, Alicja; Antoniak, Damian; Barbasiewicz, Michal
      Synthesis (2019), 51 (11), 2278-2286CODEN: SYNTBF; ISSN:1437-210X. (Georg Thieme Verlag)
      Studies on directed ortho-metalation (DoM) of arenesulfonyl fluorides (ArSO2F) with in-situ electrophile trapping were presented. Under optimized conditions (LDA, THF, -78 °), a series of model substrates was mono- and difunctionalized with trimethylsilyl chloride in good yields. The synthetic results reveal powerful directing character of the SO2F group, being ahead of bromine and methoxy substituents. Under the same metalation conditions, aryl fluorosulfates (ArOSO2F) display fragmentation to arynes and migration of the SO2F group to the ortho position (anionic thia-Fries rearrangement).
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    15. 15
      (a) Górski, B.; Talko, A.; Basak, T.; Barbasiewicz, M. Olefination with Sulfonyl Halides and Esters: Scope, Limitations, and Mechanistic Studies of the Hawkins Reaction. Org. Lett. 2017, 19, 1756– 1759,  DOI: 10.1021/acs.orglett.7b00517
      15a
      Olefination with Sulfonyl Halides and Esters: Scope, Limitations, and Mechanistic Studies of the Hawkins Reaction
      Gorski, Bartosz; Talko, Alicja; Basak, Tymoteusz; Barbasiewicz, Michal
      Organic Letters (2017), 19 (7), 1756-1759CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
      Carbanions of alkanesulfonyl halides and esters, particularly 2,2,2-trifluoroethyl sulfonates, reacted with nonenolizable carbonyl compds. (aryl aldehydes, benzophenone, trans-cinnamaldehyde) to give alkenes. Mechanistic studies reveal that initial aldol-type addn. of the carbanions is followed by cyclization and fragmentation to alkenes; the leaving group on the sulfonyl moiety controls the carbanion stability and thus the rate of olefin formation.
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      (b) Górski, B.; Basiak, D.; Talko, A.; Basak, T.; Mazurek, T.; Barbasiewicz, M. Olefination with Sulfonyl Halides and Esters: E-Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors. Eur. J. Org. Chem. 2018, 2018, 1774– 1784,  DOI: 10.1002/ejoc.201701766
      15b
      Olefination with Sulfonyl Halides and Esters: E-Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors
      Gorski, Bartosz; Basiak, Dariusz; Talko, Alicja; Basak, Tymoteusz; Mazurek, Tomasz; Barbasiewicz, Michal
      European Journal of Organic Chemistry (2018), 2018 (15), 1774-1784CODEN: EJOCFK; ISSN:1099-0690. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Carbanions of sulfonyl halides and activated sulfonates add to carbonyl compds., and so-formed aldol-type adducts spontaneously fragment into olefins. This transformation mimics the one-pot Julia olefination with (hetero)aryl sulfones, but the mechanism of fragmentation involves a four-membered intermediate, typical for reactivity of phosphorus reagents. Moreover, in contrast to the reactions of sulfones, sulfonates of fluorinated alcs. (TFE and HFI) produce byproducts that are easily removed during workup. In our report, we focus on reactions of unstabilized and semistabilized carbanion precursors: alkylsulfonates, and allyl- and benzylsulfonates, resp. In particular for semistabilized systems, olefins were synthesized as predominant E isomers in good yields. The presented studies reveal that optimal reaction conditions, including the type of base and alc. groups of the sulfonates, are different depending on stabilization of the carbanion precursors and structure of the carbonyl substrates. The practical synthetic guide is supplemented with a discussion of the mechanism, based on reactivity studies of intermediates and identification of side-products.
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      (c) Górski, B.; Basiak, D.; Grzesiński, Ł.; Barbasiewicz, M. Stereodivergent synthesis of alkenes by controllable syn-/anti-fragmentation of β-hydroxysulfonyl intermediates. Org. Biomol. Chem. 2019, 17, 7660– 7663,  DOI: 10.1039/C9OB01563A
      15c
      Stereodivergent synthesis of alkenes by controllable syn-/anti-fragmentation of β-hydroxysulfonyl intermediates
      Gorski, Bartosz; Basiak, Dariusz; Grzesinski, Lukasz; Barbasiewicz, Michal
      Organic & Biomolecular Chemistry (2019), 17 (33), 7660-7663CODEN: OBCRAK; ISSN:1477-0520. (Royal Society of Chemistry)
      The redn. of the carbonyl group in acylated trifluoroethyl alkanesulfonates follows the Felkin-Ahn selectivity, and the so-formed diastereomeric β-hydroxysulfonyl intermediates undergo syn- and anti-fragmentation, depending on the reaction conditions. In effect, isomeric E- and Z-alkenes are formed in a stereodivergent manner, which mimics the mechanistic manifold of the Peterson olefination.
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      (d) Basiak, D.; Barbasiewicz, M. Olefination with sulfonyl halides and esters – sulfur-based variant of the Horner–Wadsworth–Emmons reaction. ARKIVOC 2021, part ii, 118– 135, (a review)
      There is no corresponding record for this reference.
    16. 16
      Roman, D.; Sauer, M.; Beemelmanns, C. Applications of the Horner-Wadsworth-Emmons Olefination in Modern Natural Product Synthesis. Synthesis 2021, 53, 2713– 2739,  DOI: 10.1055/a-1493-6331
      16
      Applications of the Horner-Wadsworth-Emmons Olefination in Modern Natural Product Synthesis
      Roman, David; Sauer, Maria; Beemelmanns, Christine
      Synthesis (2021), 53 (16), 2713-2739CODEN: SYNTBF; ISSN:1437-210X. (Georg Thieme Verlag)
      A review. The application of HWE olefinations in total syntheses of structurally different natural products covering 2015 to 2020 was highlighted. Applied HWE reagents and reactions conditions are highlighted to support future synthetic approaches and serve as guideline to find the best HWE conditions for the most complicated natural products.
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    17. 17
      Hawkins, J. M.; Lewis, T. A.; Raw, A. S. Substituent Effects on Sulfonate Ester Based Olefinations. Tetrahedron Lett. 1990, 31, 981– 984,  DOI: 10.1016/S0040-4039(00)94408-3
      17
      Substituent effects on sulfonate ester based olefinations
      Hawkins, Joel M.; Lewis, Timothy A.; Raw, Andre S.
      Tetrahedron Letters (1990), 31 (7), 981-4CODEN: TELEAY; ISSN:0040-4039.
      Olefination of carbonyl compds. by the anions of sulfonate esters derived from acidic alcs. is reported. The dependence of the yield and stereochem. of olefination on the sulfonate ester's alkoxy substituent are consistent with a mechanism where apicophilic alkoxy groups promote olefination via a 10-S-5 intermediate.
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    18. 18
      (a) Kagabu, S.; Hara, K.; Takahashi, J. Alkene Formation through Condensation of Phenylmethanesulphonyl Fluoride with Carbonyl Compounds. J. Chem. Soc., Chem. Commun. 1991, 408– 410,  DOI: 10.1039/c39910000408
      18a
      Alkene formation through condensation of phenylmethanesulfonyl fluoride with carbonyl compounds
      Kagabu, Shinzo; Hara, Kenji; Takahashi, Junko
      Journal of the Chemical Society, Chemical Communications (1991), (6), 408-10CODEN: JCCCAT; ISSN:0022-4936.
      Arylmethanesulfonyl fluorides RCH2SO2F (R = Ph, 4-ClC6H4, 4-MeC6H4) condense with arom., aliph., and conjugated aldehydes and ketones R1COR2 (R1 = Ph, 4-ClC6H4, 3-O2NC6H4, PhCH2, PhCH:CH, Me2CHCH2, etc., R2 = H; R1 = R2 = Me) in the presence of potassium carbonate and dibenzo-18-crown-6 to give aryl-substituted alkenes RCH:CR1R2 in satisfactory to modest yields.
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      (b) Kagabu, S.; Shimizu, C.; Takahashi, J.; Hara, K.; Koketsu, M.; Ishida, M. Reaction of phenyl- and alkoxycarbonylmethanesulfonyl fluoride with activated haloalkanes. Bull. Soc. Chim. Fr. 1992, 129, 435– 439
      18b
      Reaction of phenyl- and alkoxycarbonylmethanesulfonyl fluoride with activated haloalkanes
      Kagabu, S.; Shimizu, C.; Takahashi, J.; Hara, K.; Koketsu, M.; Ishida, M.
      Bulletin de la Societe Chimique de France (1992), 129 (5), 435-9CODEN: BSCFAS; ISSN:0037-8968.
      Arylmethanesulfonyl fluorides, ArCH2SO2F (Ar = Ph, 4-O2NC6H4, 4-ClC6H4, 4-MeC6H4), condense with BrCH2Y (Y = COPh, COC6H4Br-4, COMe, COCMe3, CO2Et, PhCH:CH, cyano, Ph) by attacking at the methylenyl carbon instead of the carbonyl bond to give ArCH:CHY. FSO2CH2R (I, R = CO2Me, CO2Et, cyano) were prepd. by fluorination of ClSO2CH2R with KF. I (R = CO2Et) reacts with the carbonyl bonds of R1CHO (R1 = Ph, 4-ClC6H4, 2-MeC6H4, α-thienyl, α-naphthyl, CHMe2, etc.) to give R1CH:CHCO2Et, whereas it attacks the phenacyl bromide exclusively at the α-carbon to give PhCOCH:CHCO2Et. The reaction mode of these sulfonyl fluorides is discussed on the basis of kinetic data.
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    19. 19
      Perkins, C. W.; Wilson, S. R.; Martin, J. C. Ground-state analogs of transition states for attack at sulfonyl, sulfinyl, and sulfenyl sulfur: a sulfuranide dioxide (10-S-5) salt, a sulfuranide oxide (10-S-4) salt, and a sulfuranide (10-S-3) salt. J. Am. Chem. Soc. 1985, 107, 3209– 3218, and references cited therein  DOI: 10.1021/ja00297a029
      19
      Ground-state analogs of transition states for attack at sulfonyl, sulfinyl, and sulfenyl sulfur: a sulfuranide dioxide (10-S-5) salt, a sulfuranide oxide (10-S-4) salt, and a sulfuranide (10-S-3) salt
      Perkins, C. W.; Wilson, S. R.; Martin, J. C.
      Journal of the American Chemical Society (1985), 107 (11), 3209-18CODEN: JACSAT; ISSN:0002-7863.
      The prepn. and properties of anionic 10-S-5 (I), 10-S-4 (II), and 10-S-3 (III) are described. Crystallog. shows that these compds. have pseudotrigonal bipyramidal geometry in the solid state. PKa data and low-temp. NMR also support major contributions of hypervalent bonding to the ground-state structures in soln. I and II are, resp., the first examples of sulfuramide dioxide and sulfuramide oxide anions. The pKa data show that I, II, and III are more stable than their open chain analogs by at least 2.6, 5.9, and 7.5 kcal/mol, resp. The crystallog. of I, II, and III and the implications that the isolation and characterization of these salts have on the mechanisms of associative nucleophilic displacement at S are discussed.
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    20. 20
      Wagenaar, A.; Engberts, J. B. F. N. Intramolecular Nucleophilic Catalysis by the Neighboring Hydroxyl Group in Acid- and Base-Catalyzed Hydrolysis of Aromatic Sulfonamides and Sultones. Mechanism of Intramolecular Nucleophilic Substitution at Sulfonyl Sulfur. J. Org. Chem. 1988, 53, 768– 772,  DOI: 10.1021/jo00239a013
      20
      Intramolecular-catalyzed hydrolysis of sulfonamides. 10. Intramolecular nucleophilic catalysis by the neighboring hydroxyl group in acid- and base-catalyzed hydrolysis of aromatic sulfonamides and sultones. Mechanism of intramolecular nucleophilic substitution at sulfonyl sulfur
      Wagenaar, Anno; Engberts, Jan B. F. N.
      Journal of Organic Chemistry (1988), 53 (4), 768-72CODEN: JOCEAH; ISSN:0022-3263.
      A kinetic study of the cyclization of o-RR1C(OH)C6H4SO2NMe2 (R = R1 = H, Me, Et, Me2CH, Ph; R = H, R1 = Me) to sultones (I) in acid soln. showed huge rate accelerations by the gem-dialkyl groups; these accelerations increased with steric bulk. Relief of initial-state strain was the dominant factor governing the intramol. catalysis. The conjugate base of sultone II underwent a rapid degenerate rearrangement rather than conversion to a sym. pentavalent S intermediate of pseudotrigonal bipyramidal geometry. The high rate of the symmetrization reaction further illustrated the accelerating effect of the gem-dialkyl substituents. A convenient prepn. of o-alkenylbenzenesulfonamides was described.
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    21. 21
      Hohenstein, C.; Kadzimirsz, D.; Ludwig, R.; Kornath, A. Synthesis and Characterization of Tetramethylammonium Trifluorosulfate. Chem.─Eur. J. 2011, 17, 925– 929,  DOI: 10.1002/chem.201000102
      21
      Synthesis and characterization of tetramethylammonium trifluorosulfate
      Hohenstein, Christian; Kadzimirsz, Daniel; Ludwig, Ralf; Kornath, Andreas
      Chemistry - A European Journal (2011), 17 (3), 925-929CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      [Me4N]+[SO2F3]-, the 1st example of a [SO2F3]- salt, was prepd. from Me4NF and SO2F2. The colorless, microcryst. solid was characterized by its IR and Raman spectra. The trigonal bipyramidal structure of C2v symmetry of the [SO2F3]- anion is predicted by ab initio calcns. Two O atoms with d(SO) = 143.2 pm and 1 F atom with d(SF) = 157.9 pm occupy the equatorial plane. The 2 F atoms in the axial position with d(SF) = 168.5 pm are repulsed by the 2 O atoms forming a bent axis with ∠(FaxSFax) = 165.2°.
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    22. 22
      Sevenard, D. V.; Kolomeitsev, A. A.; Hoge, B.; Lork, E.; Röschenthaler, G.-V. Noncyclic [10-S-5] Sulfuranide Dioxide Salts with Three S-C Bonds: A New Class of Stable Hypervalent Compounds. J. Am. Chem. Soc. 2003, 125, 12366– 12367,  DOI: 10.1021/ja030155h
      22
      Noncyclic [10-S-5] Sulfuranide Dioxide Salts with Three S-C Bonds: A New Class of Stable Hypervalent Compounds
      Sevenard, Dmitri V.; Kolomeitsev, Alexander A.; Hoge, Berthold; Lork, Enno; Roeschenthaler, Gerd-Volker
      Journal of the American Chemical Society (2003), 125 (41), 12366-12367CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Ph triflate reacts with CF3SiMe3/Q+F- (Q+ = [K(18-crown-6)]+, Me4N+) and (Me2N)3S+Me3SiF2- to afford the first noncyclic [10-S-5] sulfuranide dioxide salts, [(CF3)3SO2]-Q+, with three S-C bonds, whose mol. structure was detd. by x-ray crystallog.
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    23. 23
      Schimler, S. D.; Cismesia, M. A.; Hanley, P. S.; Froese, R. D. J.; Jansma, M. J.; Bland, D. C.; Sanford, M. S. Nucleophilic Deoxyfluorination of Phenols via Aryl Fluorosulfonate Intermediates. J. Am. Chem. Soc. 2017, 139, 1452– 1455,  DOI: 10.1021/jacs.6b12911
      23
      Nucleophilic deoxyfluorination of phenols via aryl fluorosulfonate intermediates
      Schimler, Sydonie D.; Cismesia, Megan A.; Hanley, Patrick S.; Froese, Robert D. J.; Jansma, Matthew J.; Bland, Douglas C.; Sanford, Melanie S.
      Journal of the American Chemical Society (2017), 139 (4), 1452-1455CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      This report describes a method for the deoxyfluorination of phenols with sulfuryl fluoride (SO2F2) and tetramethylammonium fluoride (NMe4F) via aryl fluorosulfonate (ArOFs) intermediates. We first demonstrate that the reaction of ArOFs with NMe4F proceeds under mild conditions (often at room temp.) to afford a broad range of electronically diverse and functional group-rich aryl fluoride products. This transformation was then translated to a one-pot conversion of phenols to aryl fluorides using the combination of SO2F2 and NMe4F. Ab initio calcns. suggest that carbon-fluorine bond formation proceeds via a concerted transition state rather than a discrete Meisenheimer intermediate.
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    24. 24

      An alternative mechanism of the olefination may consist of reaction of aldehyde with FO2SCH(−)SO2N(+)R3, formed via elimination of fluoride and addition of N-methylpyrrolidine.

      There is no corresponding record for this reference.
    25. 25
      Fild, M.; Rieck, H.-P. Darstellung von α-substituierten Methansulfonsäurechloriden. Chem.-Ztg. 1976, 100, 391– 392
      25
      Production of α-substituted methanesulfonic acid chlorides
      Fild, Manfred; Rieck, Hans P.
      Chemiker-Zeitung (1976), 100 (9), 391-2CODEN: CMKZAT; ISSN:0009-2894.
      RCH(SO2Cl)2 (I; R = H, Cl) were prepd. by the reaction of a RCH2CO2H with ClSO3H. Thus, reaction of 1:2:2 mixts. of RCH2CO2H (R = H, Cl), ClSO3H, and POCl3 at 105-10° gave 75% I (R = H) (II) and 65% I (R = Cl), resp. Reaction of (HO)2P(O)CH2CO2H with ClSO3H and POCl3 at 90° gave 60% ClSO2CH2P(O)Cl2. Chlorination of II with N-chlorosuccinimide and SOCl2 gave 86% Cl2C(SOCl2)2.
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    26. 26
      Sartori, P.; Jüschke, R. Zur Synthese von Halogenmethandisulfonylfluoriden. J. Fluorine Chem. 1994, 69, 157– 162,  DOI: 10.1016/0022-1139(94)03072-3
      26
      Synthesis of halomethanedisulfonyl fluorides
      Sartori, Peter; Jueschke, Ralf
      Journal of Fluorine Chemistry (1994), 69 (2), 157-62CODEN: JFLCAR; ISSN:0022-1139. (Elsevier)
      The reaction of methanedisulfonyl difluoride with an N-halosuccinimide gave dihalomethanedisulfonyl difluorides. The hitherto unknown monohalogenomethanedisulfonyl fluorides can be prepd. by the treatment of potassium or silver bis[(trifluoromethyl)sulfonyl]methanide with chlorine, bromine and iodine. The related fluorine derivs. were obtained by the electrochem. fluorination of methanedisulfonyl fluoride in anhyd. HF. Besides the known difluoromethanedisulfonyl fluoride, fluoromethanedisulfonyl fluoride could be isolated as a byproduct.
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    27. 27

      See the Supporting Information for details.

      There is no corresponding record for this reference.
    28. 28
      Dong, Z.; Chen, Y.; Yang, Z.; Yang, Z.; Xu, J. A Tandem Sulfonylation and Knoevenagel Condensation for the Preparation of Sulfocoumarin-3-carboxylates. Synthesis 2019, 51, 1809– 1818,  DOI: 10.1055/s-0037-1611703
      28
      A Tandem Sulfonylation and Knoevenagel Condensation for the Preparation of Sulfocoumarin-3-carboxylates
      Dong, Ziyang; Chen, Yang; Yang, Zhiheng; Yang, Zhanhui; Xu, Jiaxi
      Synthesis (2019), 51 (8), 1809-1818CODEN: SYNTBF; ISSN:1437-210X. (Georg Thieme Verlag)
      Herein, a simple, one-pot procedure for the synthesis of structurally diverse sulfonocoumarin-3-carboxylates I (R1 = H, 7-OMe, 6-F, etc.) by heating 2-hydroxyaryl aldehydes with an active sulfonyl chlorides in the presence of pyridine is described. The process tolerates numerous functional groups including alkoxy, alkyl, halogen, nitro, and even nucleophilic phenolic hydroxy. Addnl., reactions of 2-hydroxyaryl ketones and 2-methylaminoaryl aldehydes give 4-substituted sulfocoumarins and 1-aza-2-sulfocoumarins, resp. A gram-scale synthesis and further derivatizations are also reported. The ester group is easily removed via Happer's decarboxylation.
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    29. 29
      Tanc, M.; Carta, F.; Scozzafava, A.; Supuran, C. T. 6-Substituted 1,2-benzoxathiine-2,2-dioxides are isoform-selective inhibitors of human carbonic anhydrases IX, XII and VA. Org. Biomol. Chem. 2015, 13, 77– 80, and references cited therein  DOI: 10.1039/C4OB02155J
      29
      6-Substituted 1,2-benzoxathiine-2,2-dioxides are isoform-selective inhibitors of human carbonic anhydrases IX, XII and VA
      Tanc, Muhammet; Carta, Fabrizio; Scozzafava, Andrea; Supuran, Claudiu T.
      Organic & Biomolecular Chemistry (2015), 13 (1), 77-80CODEN: OBCRAK; ISSN:1477-0520. (Royal Society of Chemistry)
      A series of 6-substituted 2-benzoxathiine-2,2-dioxides were synthesized starting from 2,5-dihydroxybenzaldehyde, and then screened in vitro for their inhibition properties against five human carbonic anhydrase (hCA, EC 4.2.1.1) isoforms. All the compds. showed excellent selectivity against the mitochondrial (hCA VA) and the tumor assocd. (hCA IX and XII) enzymes.
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    30. 30
      Maletina, I. I.; Mironova, A. A.; Savina, T. I.; Yagupolskii, Y. L. Methanedisulfofluoride. Zh. Org. Chim. 1979, 15, 2416– 2417
      30
      Methanedisulfonyl difluoride
      Maletina, I. I.; Mironova, A. A.; Savina, T. I.; Yagupol'skii, Yu. L.
      Zhurnal Organicheskoi Khimii (1979), 15 (11), 2416-17CODEN: ZORKAE; ISSN:0514-7492.
      Treating CH2(SO2Cl)2 with anhyd. ZnF2 or AgF at 100° gave CH2(SO2F)2 (I) in 82 and 57.4% yield, resp. I condensed with p-Me2NC6H4CHO, RC6H4I(OAc)2 (R = H, m-O2N) and Me2SO to give 84% p-Me2NC6H4CH:C(SO2F)2, 89-93% RC6H4I:C(SO2F)2 (same R) and 83% Me2S:C(SO2F)2, resp.
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    31. 31
      Zhang, Z.-W.; Wang, S.-M.; Fang, W.-Y.; Lekkala, R.; Qin, H.-L. Protocol for Stereoselective Construction of Highly Functionalized Dienyl Sulfonyl Fluoride Warheads. J. Org. Chem. 2020, 85, 13721– 13734,  DOI: 10.1021/acs.joc.0c01877
      31
      Protocol for Stereoselective Construction of Highly Functionalized Dienyl Sulfonyl Fluoride Warheads
      Zhang, Zai-Wei; Wang, Shi-Meng; Fang, Wan-Yin; Lekkala, Ravindar; Qin, Hua-Li
      Journal of Organic Chemistry (2020), 85 (21), 13721-13734CODEN: JOCEAH; ISSN:0022-3263. (American Chemical Society)
      A pyrrolidine-mediated Knoevenagel-type reaction for highly stereoselective construction of novel α-halo-1,3-dienylsulfonyl fluorides was achieved in up to 100% Z-selectivity and high yields at room temp. from condensation of the readily available aldehydes and halomethanesulfonyl fluorides. This protocol provided a class of unique α-halo-1,3-dienylsulfonyl fluorides with wide scope and excellent functional group compatibility. The α-halo-1,3-dienylsulfonyl fluorides were used as versatile building blocks in sulfur fluoride exchange click chem., Suzuki reaction, and Sonogashira reaction for the assembly of highly functionalized dienyl sulfonyl fluoride derivs. to be applied as covalent warheads for the discovery of new drugs.
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    32. 32
      (a) Yanai, H.; Egawa, S.; Taguchi, T. Reductive alkylation of bis(triflyl)methane through self-promoting formation of easily isolable 1,1-bis(triflyl)alkenes. Tetrahedron Lett. 2013, 54, 2160– 2163,  DOI: 10.1016/j.tetlet.2013.02.039
      32a
      Reductive alkylation of bis(triflyl)methane through self-promoting formation of easily isolable 1,1-bis(triflyl)alkenes
      Yanai, Hikaru; Egawa, Saki; Taguchi, Takeo
      Tetrahedron Letters (2013), 54 (17), 2160-2163CODEN: TELEAY; ISSN:0040-4039. (Elsevier Ltd.)
      A convenient and practical synthesis of 1,1-bis(triflyl)alkenes, e.g. I [Ar = Ph, 4-MeC6H4, 2-BrC6H4, etc.; Tf = triflyl] via self-promoting condensation of Tf2CH2 and aldehydes was developed and chem. behavior of these alkenes was investigated. Among the alkenes, easily isolable 1,1-bis(triflyl)alkadienes derived from α,β-unsatd. aldehydes could be used as useful building blocks for 1,1-bis(triflyl)alkanes. The 1,1-bis(triflyl)alkane thus obtained showed catalyst activity in the acetal forming reaction, which is a typical reaction catalyzed by Bronsted acids.
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      (b) Yanai, H.; Takahashi, R.; Takahashi, Y.; Kotani, A.; Hakamata, H.; Matsumoto, T. 2-(Pyridinium-1-yl)-1,1-bis(perfluoroalkylsulfonyl)ethan-1-ide: A Practical Reagent for Synthesis of Strongly Acidic 1,1-Bis(perfluoroalkylsulfonyl)alkanes. Chem.─Eur. J. 2017, 23, 8203– 8211,  DOI: 10.1002/chem.201700515
      32b
      2-(Pyridinium-1-yl)-1,1-bis(perfluoroalkylsulfonyl)ethan-1-ide: A Practical Reagent for Synthesis of Strongly Acidic 1,1-Bis(perfluoroalkylsulfonyl)alkanes
      Yanai, Hikaru; Takahashi, Ryuta; Takahashi, Yoichi; Kotani, Akira; Hakamata, Hideki; Matsumoto, Takashi
      Chemistry - A European Journal (2017), 23 (34), 8203-8211CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      On mixing (RfSO2)2CH2 (Rf=perfluoroalkyl), paraformaldehyde, and substituted pyridines, a three-component reaction proceeded smoothly to give unusual zwitterions bearing both pyridinium and stabilized carbanion moieties in good to excellent yields [e.g., Tf2CH2 + (CH2O)n + pyridine → I (quant.)]. Of these, 2-fluoropyridinium derivs. rapidly dissocd. in acetonitrile to give equil. mixts. of the zwitterions and (RfSO2)2C=CH2/2-fluoropyridine, as confirmed by detailed variable-temp. NMR studies. The dynamic behavior of such 2-fluoropyridinium compds. allows them to be used as shelf-stable, easy-to-handle sources of (RfSO2)2C=CH2. With these reagents, strongly acidic carbon acids (RfSO2)2CHR were synthesized, which served as a new type of acid catalysts. Moreover, C-C bond-forming reactions with a ketene silyl acetal proceeded efficiently with Tf2C=CH2 generated in situ.
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    33. 33
      Koppel, I. A.; Koppel, J.; Pihl, V.; Leito, I.; Mishima, M.; Vlasov, V. M.; Yagupolskii, L. M.; Taft, R. W. Comparison of Brønsted acidities of neutral CH acids in gas phase and dimethyl sulfoxide. J. Chem. Soc., Perkin Trans. 2 2000, 1125– 1133,  DOI: 10.1039/b001792m
      There is no corresponding record for this reference.
    34. 34
      Zhu, Z.-S. Synthesis and Reactions of 1-Aryl-2,2-bis(perfluoroalkanesulfonyl)ethylenes. Synthesis 1994, 1994, 261– 263,  DOI: 10.1055/s-1994-25454
      There is no corresponding record for this reference.
    35. 35
      Chen, Q.; Mayer, P.; Mayr, H. Ethenesulfonyl Fluoride: The Most Perfect Michael Acceptor Ever Found?. Angew. Chem., Int. Ed. 2016, 55, 12664– 12667,  DOI: 10.1002/anie.201601875
      35
      Ethenesulfonyl Fluoride: The Most Perfect Michael Acceptor Ever Found?
      Chen, Quan; Mayer, Peter; Mayr, Herbert
      Angewandte Chemie, International Edition (2016), 55 (41), 12664-12667CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The kinetics of the reactions of ethenesulfonyl fluoride (ESF) with sulfonium and pyridinium ylides were measured photometrically to det. the electrophilicity parameter of ESF according to the correlation lg k20 °C=sN(N+E). With E=-12.09, ESF is among the strongest Michael acceptors in our comprehensive electrophilicity scale, which explains its excellent performance in reactions with many nucleophiles. Its predicted usability as a reagent in electrophilic arom. substitutions with electron-rich arenes was confirmed by uncatalyzed reactions with alkyl-substituted pyrroles.
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    36. 36
      Yanai, H.; Takahashi, Y.; Fukaya, H.; Dobashi, Y.; Matsumoto, T. 2-(Pyridinium-1-yl)-1,1-bis(triflyl)ethanides: structural behaviour and availability as bis(triflyl)ethylating reagents. Chem. Commun. 2013, 49, 10091– 10093,  DOI: 10.1039/c3cc46171h
      36
      2-(Pyridinium-1-yl)-1,1-bis(triflyl)ethanides: structural behaviour and availability as bis(triflyl)ethylating reagents
      Yanai, Hikaru; Takahashi, Yoichi; Fukaya, Haruhiko; Dobashi, Yasuo; Matsumoto, Takashi
      Chemical Communications (Cambridge, United Kingdom) (2013), 49 (86), 10091-10093CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      Stable and easy-to-handle zwitterions contg. carbanion and pyridinium moieties were synthesized, and their structural studies by both X-ray crystallog. and theor. methods revealed the stereoelectronic effect in the zwitterionic 'C--C-N+' system.
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    37. 37
      (a) Klöter, G.; Pritzkow, H.; Seppelt, K. Tris(fluorosulfonyl)methane, HC(SO2F)3. Angew. Chem., Int. Ed. 1980, 19, 942– 942,  DOI: 10.1002/anie.198009421
      There is no corresponding record for this reference.
      (b) Winter, R.; Gard, G. L.; Mews, R.; Noltemeyer, M. Anionic derivatives of pentafluoro-λ6-sulfanyl(fluorosulfonyl) acetic acid esters. J. Fluorine Chem. 1993, 60, 109– 123,  DOI: 10.1016/S0022-1139(00)80025-1
      37b
      Anionic derivatives of pentafluoro-λ6-sulfanyl (fluorosulfonyl) acetic acid esters
      Winter, R.; Gard, G. L.; Mews, R.; Noltemeyer, M.
      Journal of Fluorine Chemistry (1993), 60 (2-3), 109-23CODEN: JFLCAR; ISSN:0022-1139.
      New ester salts [R3NH]+[F5SC(SO2F)CO2R1]- (R = H, Et; R1 = Me, Me2CH) have been prepd. from corresponding esters and amines. Na[F5SC(SO2F)CO2CHMe2] was used to prep. α-substituted derivs. F5SCX(SO2F)CO2CHMe2 (X = Br, Cl). The crystal structure of [Et3NH]+[F5SC(SO2F)CO2Me]- was detd. and is monoclinic.
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      (c) Filatov, A. A.; Boiko, V. N.; Yagupolskii, Y. L. Interaction of 2,4,6-tris(fluorosulfonyl)chlorobenzene with O-N-, S-, C-nucleophiles and F-anion. J. Fluorine Chem. 2012, 143, 123– 129,  DOI: 10.1016/j.jfluchem.2012.05.015
      37c
      Interaction of 2,4,6-tris(fluorosulfonyl)chlorobenzene with O-, N-, S-, C-nucleophiles and F-anion
      Filatov, Andrey A.; Boiko, Vladimir N.; Yagupolskii, Yurii L.
      Journal of Fluorine Chemistry (2012), 143 (), 123-129CODEN: JFLCAR; ISSN:0022-1139. (Elsevier B.V.)
      Reactions of 2,4,6-tris(fluorosulfonyl)chlorobenzene (I) with O-, N-, S-, and C-nucleophiles and fluoride anion showed high reactivity of I that was defined by three strong electron-withdrawing SO2F groups creating several electrophilic centers within the mol. Conditions for selective chlorine atom substitution were defined that resulted in formation of the corresponding ethers, amines, and sulfides, while an excess of the nucleophile commonly led to all of the SO2F groups being substituted as well. Two equivalents of fluoride-anion source not only gave rise to to the chlorine-fluorine substitution but also afforded an anionic σ-complex with two fluorine atoms in the sp3 carbon atom position. Redn. of chlorobenzene I with zinc/AcOH was found to provide a convenient method for 1,3,5-tris(fluorosulfonyl)benzene prepn.
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  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.orglett.2c01604.

    • Experimental procedures, characterization data, and NMR spectra reproductions of the synthesized compounds (PDF)

    Accession Codes

    CCDC 2161680–2161683 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.


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