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Synthesis of Fluorosugar Reagents for the Construction of Well-Defined Fluoroglycoproteins

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† Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, C/Marcel·lí Domingo s/n, 43007 Tarragona, Spain
‡ Department of Chemistry, University of Cambridge, Lensfield Road, CB2 1EW Cambridge, U.K.
§ Instituto de Medicina Molecular, Faculdade de Medicina da Universidade de Lisboa, Av. Prof. Egas Moniz, 1649-028 Lisboa, Portugal
Cite this: Org. Lett. 2015, 17, 11, 2836-2839
Publication Date (Web):May 22, 2015
https://doi.org/10.1021/acs.orglett.5b01259
Copyright © 2015 American Chemical Society
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Abstract

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2-Deoxy-2-fluoroglycosyl iodides are privileged glycosyl donors for the stereoselective preparation of 1-Nu-β-fluorosugars, which are useful reagents for chemical site-selective protein glycosylation. Ready access to such β-fluorosugars enables the mild and efficient construction of well-defined fluoroglycoproteins.

F-glycopeptides(1-9) and the more recently disclosed F-glycoproteins(10-19) are promising candidates for the preparation of synthetic carbohydrate vaccines(20) and hold great potential as a new generation of [18F]-(glyco)radiopharmaceuticals(21, 22) and tracers for the noninvasive imaging techniques positron emission tomography (18F-PET)(23, 24) and magnetic resonance/magnetic resonance imaging (19F-MR/MRI).(25) In addition to the development of more efficient methods for protein/peptide modification,(26) it is also pivotal to access pure F-sugar reagents and building blocks for such transformations. These glycosyl units typically include in their structure reactive handles such as azides (for copper(I)-catalyzed azide–alkyne cycloaddition–CuAAC and Staudinger ligations)(17) or chalcogens in the form of sulfhydryl groups or diselenide moieties (for exchange reactions with Cys or additions to dehydroalanine),(14, 15) which upon reaction generate a new carbohydrate–protein conjugate. Retrosynthetic analysis revealed that 2-F-glycosyl halides are suitable glycosyl donors for the preparation of such reagents via biphasic glycosylations/phase-transfer catalyzed reactions (PTC). These moieties enable exquisite control of β-anomeric selectivity (via SN2-like mechanism) during the introduction of the reactive handle, which is typically a “soft” nucleophilic moiety.(27) There are two general strategies (one-pot from glycals vs two-step from 2-F-pyranoses) for the preparation of 1-β-“soft Nu”-2-deoxy-2-fluoroglycosides using electrophilic F+ reagents (Scheme 1).(28) While the one-pot strategy works well for certain configurations (e.g., Gal), the two-step approach is more general and thus preferred for the preparation of pure F-sugar reagents in a more efficient and homogeneous manner (giving a better overall yield and controlled Fax/eq diastereoselectivity).

Scheme 1

Scheme 1. General Strategies for the Preparation of 1-β-“Soft Nu”-2-deoxy-2-fluoroglycosides Using F+
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Among glycosyl halides, iodides(29) have been recently utilized in several glycosylation strategies and provide a robust platform for PTC reactions, perhaps leading to higher yields compared to chlorides or bromides due to their superior leaving group properties under SN2-like reaction conditions. There are very few examples of 2-F- and 2,2-diF-glycosyl iodides. This rare class of glycosyl donors include some isolated examples of 2-F- and 2,2-diF-pyranosides(30-32) and our 2-F-galactopyranosyl iodide prepared via a “one-pot” strategy, as revealed by VT-NMR experiments (see Supporting Information),(33) and more recently 2,2-diF-furanosides.(34) Despite their great potential, low preparative yields in the pyranose series and inseparable α/β mixtures in the case of furanoses has so far hampered their wide utilization as β-selective glycosyl donors in PTC protocols.

In this work, we envisioned a “two-step” strategy for the preparation of 2-F-glycosyl iodides from ready available 2-F-glycosyl-1-O-Ac derivatives that might overcome such limitations enabling a more efficient preparation of this class of highly reactive glycosyl donors. We then sought to explore their reactivity for the preparation of fluorosugar reagents that would serve as useful moieties to achieve site-selective chemical glycosylation of proteins. We first evaluated the reaction conditions using 2-F-α/β-galactopyranose 1 (Table 1). Initial experiments revealed TMSI(35) to be an effective promoter for the preparation of glycosyl iodide 2a, although the reaction only proceeded in 57% yield after two consecutive reaction cycles (entry 1). We found that addition of MgO(36) that acts as a scavenger for the in situ generated TMSOAc avoids the reversible formation of starting 1, while increasing the yields up to 78% (entry 2). Good yields (up to 85% in a single reaction cycle) were finally obtained by increasing the amount of both TMSI (2.2 equiv) and MgO (4 equiv) as well as reducing the reaction temperature (from reflux to rt) in order to avoid detrimental side reactions (entry 3). Other promoters were also evaluated (entries 4–7). While the use of HMDS/I2 proved ineffective and complex mixtures of products were observed (entry 7),(37) the in situ formation of highly reactive HI by refluxing AcSH and I2 allowed the formation of the desired iodide 2a, albeit in lower yields compared to TMSI (up to 54%) (entries 4–6).(38) Interestingly, the use of MgO was found to be costly (24%) when using AcSH and I2 probably due to its incompatibility with AcSH and/or HI (entry 4). 2-F-galactosyl bromide 2b was also prepared following a reported procedure in 95% yield (Table 1, entry 8).(39) With the optimized conditions in hand we set out to evaluate the scope of the iodination with other configurations (Table 2). Conditions A (with TMSI) were utilized with 2-F-α/β-pyranoses of Glc3 and Man4 configuration affording desired glycosyl iodides 5a and 6a in moderate yields (entries 1 and 4). To our delight, conditions B (with AcSH and I2) improved the yield to 82% for 5a and 75% for 6a (entries 2 and 5). 2-F-glycosyl bromides 5b and 6b were also prepared in excellent yields (up to 98%) using the standard conditions (entries 3 and 6). Practical yields of the corresponding α-glycosyl iodides as sole anomers (e.g., 1JC1–H1 = 187.6 Hz, 3J1,2 = 4.7 Hz, and 3J3,4 = 10.2 Hz in 5a, 4C1 conformation)(40) were obtained regardless of the pyranoside configuration (Gal, Glc, and Man).

Table 1. Optimization of Reaction Conditions for the Halogenation of 1a
entryconditions (equiv)productyield (%)
1TMSI (1), rt, 8 h2a57b
2TMSI (1.1), MgO (2), reflux, 12 h2a78b
3TMSI (2.2), MgO (4), rt, 24 h2a85
4AcSH (1.7), I2 (0.8), MgO (2), reflux, 30 h2a24b
5AcSH (4.4), I2 (2), reflux, 12 h2a34b
6AcSH (2.2), I2 (1), reflux, 12 h2a54b
7HMDS (0.6), I2 (0.6), rt, 24 h2amixture
833% HBr in AcOH, rt, 8 h2b95
a

General conditions: 2-F-α/β-galactopyranose 1 (2:1 α/β) (1 equiv) in dry CH2Cl2 (0.1 M) unless otherwise indicated.

b

Isolated yield after two consecutive reaction cycles. TMS = trimethylsilyl, HMDS = hexamethyldisilazane.

Table 2. Scope of Halogenationa
entry2-F-pyranoseconditionsproductyield (%)
13A5a38b
23B5a82b
33C5b98
44A6a50b
54B6a75b
64C6b94
a

General conditions: 2-F-α/β-pyranose (1:0–1:3 α/β) (1 equiv) in dry CH2Cl2 (0.1 M) unless otherwise indicated.

b

Isolated yield after two consecutive reaction cycles. Conditions A: TMSI (2.2 equiv), MgO (4 equiv), rt, 30 h. Conditions B: AcSH (2.2), I2 (1), reflux, 5 h. Conditions C: 33% HBr in AcOH, rt, 3–8 h. TMS = trimethylsilyl.

2-F-glycosyl iodides proved stable and were purified by SiO2 flash column chromatography with no decomposition observed. They are also UV visible (at 254 nm) providing an easy experimental follow-up. Similar to other protocols that use strong acid activators (e.g., HBr), base sensitive acetyl groups are the more appropriate protecting groups for the overall synthetic route (Selectfluor–halogenation–PTC–deprotection). Acetyl protecting groups are easily introduced, prove stable under the sequence of transformations, and are easily removed under Zemplén conditions to afford the final unprotected and ready-to-conjugate fluorosugar reagents. Other acid sensitive groups such as tert-butyldiphenylsilyl (TBDPSi) were not tolerated under the optimized acid–based reaction conditions, and extensive deprotection was observed.

Next, the synthesis of 1-β-“soft Nu”-2-deoxy-2-fluoroglycosides was attempted using 2-F-glycosyl halides 2a,b and 5–6a,b (Scheme 2). A wide range of N-, S-, and Se-nucleophiles led to β-fluorosugar reagents 7–10, useful for chemical protein glycosylation strategies,(14, 15, 17) even including those with the challenging 1-β-cis-Man(41) disposition 9a–c. Excellent yields (up to 98%) and pure β-selectivity (e.g., 1JC1–H1 = 162.7 Hz, 3J1,2 = 10.6 Hz, and 3J3,4 = 9.5 Hz in 8c, 4C1 conformation)(40) were always obtained. Iodides proved slightly better in terms of yield (ca. 10–15%) over their bromide counterparts using a better Nu in a “match” scenario of reactivity. We believe the low reactivity of mannosyl-1-halides is probably due to unfavorable dipolar interactions between the donor and the incoming Nu and/or conformational issues that reduce the reaction rate. This made competitive otherwise negligible side reactions that reduce the overall yield.(42) A weaker Nu such as sodium benzenethiosulfonate (NaPTS)(43) necessitated the use of more reactive iodides and afforded moderate-to-good yields (88% for I vs 45% for Br in 10a). Our data indicate that 2-F-glycosyl iodides are needed when using weaker nucleophiles. The reported 2-F-glycosyl iodides may also find broader utility for example in the preparation of advanced fluorinated building blocks such as O-linked natural product mimetics(44)11a and covalent inhibitors(45, 46) of carbohydrate processing enzymes 11b and 12 where the use of “soft” nucleophilic acceptors are required. Finally, to illustrate the application of such reagents and further complement our previous reports on the preparation of a variety of well-defined triazole,(17) thioether,(15, 18) and SeS-linked(14, 18) fluorinated glycoproteins including their [18F]-counterparts, we examined the reaction between Cys-specific Ac3GlcF(9) and Ac3GalF-1-PTS reagents 10a,b with Annexin V 13. This protein displays a unique naturally occurring surface exposed Cys and is widely utilized as a marker of apoptosis (Scheme 3).(47) Indeed, reaction of 10a or 10b with Annexin V 13 in 20 mM Tris HCl buffer pH 8 and 10% CH3CN, which was used to ensure reagent solubility, gave the expected homogeneous disulfide-linked F-glycoproteins 14a,b in >95% conversion after 1 h at rt. This is demonstrative of the utility of the reagents that can now be easily prepared from the 2-F-glycosyl iodide reagents we have reported in this work. Moreover, this methodology is amenable to utilization in 18F-PET imaging using the corresponding [18F]-glyco-1-PTS reagents.(9)

Scheme 2

Scheme 2. Phase-Transfer Catalyzed Reactions (PTC) for the Preparation of 7–12a
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aGeneral conditions: 2-F-α-pyranosyl halide (1 equiv), Nu (2 equiv), TBAHS (2 equiv) in 5:1 EtOAc–1 M Na2CO3 aq (0.04 M), rt, from 1 h up to 7 days unless otherwise indicated.

Determined by 19F NMR of the crude reaction mixture.

2-F-α-galactosyl bromide 2b (1 equiv), Nu (2 equiv), TBAB (2 equiv) in 3:2 CH2Cl2–5% NaOH aq (0.02 M), rt, 14–22 h.

2-F-α-galactosyl bromide 2b (2 equiv), estrone (1 equiv), 60% NaH in mineral oil (1.5 equiv) in dry 1,4-dioxane (0.08 M), rt, 24 h. Nu = nucleophile. TBAHS = tetrabutylammonium hydrogen sulfate. TBAB = tetrabutylammonium bromide.

Scheme 3

Scheme 3. Selective Chemical Protein Modification of Annexin V 13a
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aGeneral conditions: Annexin V 13 (1 mg mL–1) (1 equiv), 2-F-sugar reagent 10a,b (250 equiv) in 20 mM Tris HCl buffer (pH 8.0) and 10% CH3CN, rt, 1 h.

In summary, we have disclosed a general strategy for accessing a wide range of 1-Nu-2-fluorosugars that are useful reagents for chemical-site-selective protein glycosylation. The glycosyl iodide intermediates prepared here possess a seemly balance between stability and reactivity that facilitates their preparation, purification, and storage. Importantly, these intermediates also ensure product homogeneity by their exquisite β-control during stereoselective glycosylation with a “soft” Nu (via SN2-like reactions). The reported F-sugar reagents will find broad utility for building not only homogeneous 19F- but also [18F]-glycoprobes that are valuable tools in the fields of chemical biology and biomedical imaging.

Supporting Information

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Experimental details, VT-NMR experiments, characterization data, and copies of 1H, 13C, and 19F NMR spectra for all new compounds. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.orglett.5b01259.

The authors declare no competing financial interest.

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Acknowledgment

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We thank the European Commission (Marie Curie CIG, O.B. and G.J.L.B.), MICINN, Spain (Juan de la Cierva Fellowship, O.B.), MINECO, Spain (CTQ2011-22872BQU), and Generalitat de Catalunya (M.S.) for generous financial support. We also thank Mr. Adrià Cardona-Benages (URV) for technical assistance. G.J.L.B. thanks the Royal Society (University Research Fellowship), Fundação para a Ciência a Tecnologia, Portugal (FCT Investigator), and the EPSRC for funding.

References

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    3,4,5-Tri-O-acetyl-2-[18F]fluoro-2-deoxy-D-glucopyranosyl 1-phenylthiosulfonate (I) was developed as a thiol-reactive labeling reagent for the site-specific 18F-glycosylation of peptides. Starting from 1,3,4,6-tetra-O-acetyl-2-deoxy-2-[18F]fluoroglucopyranose, a three-step radiochem. pathway was investigated and optimized, and I was obtained in a radiochem. yield of about 33% in 90 min (decay-cor. and based on starting [18F]fluoride). I was reacted with the model pentapeptide CAKAY, providing chemoselectivity and excellent conjugation yields of >90% under mild reaction conditions. The optimized method was adopted to the 18F-glycosylation of the αvβ3-affine peptide cyclo(RGDfC), achieving high conjugation yields (95%, decay-cor.). The αvβ3 binding affinity of the glycosylated cyclo(RGDfC) remained uninfluenced as detd. by competition binding studies vs. 125I-echistatin using both isolated αvβ3 and human umbilical vein endothelial cells (Ki = 68 ± 10 nM (αvβ3) vs. Ki = 77 ± 4 nM (HUVEC)). The whole radiosynthetic procedure, including the prepn. of I, peptide ligation, and final HPLC purifn., provided a decay-uncorrected radiochem. yield of 13% after a total synthesis time of 130 min. I can be used to prep. 18F-labeled bioactive S-glycopeptides for studying their pharmacokinetics in vivo by positron emission tomog. (PET).
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    Huo, C.-X.; Zheng, X.-J.; Xiao, A.; Liu, C.-C.; Sun, S.; Lv, Z.; Ye, X.-S. Org. Biomol. Chem. 2015, 13, 3677– 3690
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    Synthetic and immunological studies of N-acyl modified S-linked STn derivatives as anticancer vaccine candidates
    Huo, Chang-Xin; Zheng, Xiu-Jing; Xiao, An; Liu, Chang-Cheng; Sun, Shuang; Lv, Zhuo; Ye, Xin-Shan
    Organic & Biomolecular Chemistry (2015), 13 (12), 3677-3690CODEN: OBCRAK; ISSN:1477-0520. (Royal Society of Chemistry)
    It is well known that tumor cells express some aberrant glycans, termed tumor-assocd. carbohydrate antigens (TACAs). TACAs are good targets for the development of carbohydrate-based anticancer vaccines. However, one of the major problems is that carbohydrate antigens possess a weak immunogenicity. To tackle this problem, a no. of unnatural N-modified S-linked STn analogs were designed and prepd. Reaction of the modified STn disaccharides with bifunctional adipic acid p-nitrophenyl diester provided the corresponding activated esters, which was followed by the conjugation with keyhole limpet hemocyanin (KLH), affording the corresponding protein conjugates. The immunol. properties of these glycoconjugates were evaluated in a mouse model. The results showed that the modified glycoconjugates stimulated the prodn. of IgG antibodies that are capable of recognizing the naturally occurring STn antigen, helping the discovery of carbohydrate-based anticancer vaccine candidates.
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    Lee, H.-Y.; Chen, C.-Y.; Tsai, T.-I.; Li, S.-T.; Lin, K.-H.; Cheng, Y.-Y.; Ren, C.-T.; Cheng, T.-J. R.; Wu, C.-Y.; Wong, C.-H. J. Am. Chem. Soc. 2014, 136, 16844– 16853
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    Immunogenicity study of Globo H analogues with modification at the reducing or nonreducing end of the tumor antigen
    Lee, Hsin-Yu; Chen, Chien-Yu; Tsai, Tsung-I.; Li, Shiou-Ting; Lin, Kun-Hsien; Cheng, Yang-Yu; Ren, Chien-Tai; Cheng, Ting-Jen R.; Wu, Chung-Yi; Wong, Chi-Huey
    Journal of the American Chemical Society (2014), 136 (48), 16844-16853CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Globo H-based therapeutic cancer vaccines have been tested in clin. trials for the treatment of late stage breast, ovarian, and prostate cancers. In this study, we explored Globo H analog antigens with an attempt to enhance the antigenic properties in vaccine design. The Globo H analogs with modification at the reducing or nonreducing end were synthesized using chemoenzymic methods, and these modified Globo H antigens were then conjugated with the carrier protein diphtheria toxoid cross-reactive material (CRM) 197 (DT), and combined with a glycolipid C34 as an adjuvant designed to induce a class switch to form the vaccine candidates. After Balb/c mice injection, the immune response was studied by a glycan array and the results showed that modification at the C-6 position of reducing end glucose of Globo H with the fluoro, azido, or Ph group elicited IgG antibody response to specifically recognize Globo H (GH) and the GH-related epitopes, stage-specific embryonic antigen 3 (SSEA3) (also called Gb5) and stage-specific embryonic antigen 4 (SSEA4). However, only the modification of Globo H with the azido group at the C-6 position of the nonreducing end fucose could elicit a strong IgG immune response. Moreover, the antibodies induced by these vaccines were shown to recognize GH expressing tumor cells (MCF-7) and mediate the complement-dependent cell cytotoxicity against tumor cells. Our data suggest a new potential approach to cancer vaccine development.
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    Orwenyo, J.; Huang, W.; Wang, L. X. Bioorg. Med. Chem. 2013, 21, 4768– 4777
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    Chemoenzymatic synthesis and lectin recognition of a selectively fluorinated glycoprotein
    Orwenyo, Jared; Huang, Wei; Wang, Lai-Xi
    Bioorganic & Medicinal Chemistry (2013), 21 (16), 4768-4777CODEN: BMECEP; ISSN:0968-0896. (Elsevier B.V.)
    A chemoenzymic glycosylation remodeling method for the synthesis of selectively fluorinated glycoproteins is described. The method consists of chem. synthesis of a fluoroglycan oxazoline and its use as donor substrate for endoglycosidase (ENGase)-catalyzed transglycosylation to a GlcNAc-protein to form a homogeneous fluoroglycoprotein. The approach was exemplified by the synthesis of fluorinated glycoforms of RNase B. An interesting finding was that fluorination at the C-6 of the 6-branched mannose moiety in the Man3GlcNAc core resulted in significantly enhanced reactivity of the substrate in enzymic transglycosylation. A structural anal. suggests that the enhancement in reactivity may come from favorable hydrophobic interactions between the fluorine and a tyrosine residue in the catalytic site of the enzyme (Endo-A). SPR anal. of the binding of the fluorinated glycoproteins with lectin Con A (con A) revealed the importance of the 6-hydroxyl group on the α-1,6-branched mannose moiety in con A recognition. The present study establishes a facile method for prepn. of selectively fluorinated glycoproteins that can serve as valuable probes for elucidating specific carbohydrate-protein interactions.
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    2,2,2-Trifluoroethyl 6-thio-β-D-glucopyranoside as a selective tag for cysteines in proteins
    Frohlich Richard F G; Schrank Evelyne; Zangger Klaus
    Carbohydrate research (2012), 361 (), 100-4 ISSN:.
    A synthetic route to a trifluoromethyl and thiol containing glucose derivative (2,2,2-trifluoroethyl 6-thio-β-D-glucopyranoside) is presented, which is based on microwave-assisted Fischer glycosylation under increased pressure. This water-soluble, neutral thiol-compound can be used to selectively introduce a fluorine probe for (19)F NMR spectroscopy on cysteines in proteins. It can be attached under mild conditions in an aqueous environment without the risk of denaturing the protein. This tag has been applied to determine the redox-state of two cysteine residues in a bacterial transcription activator. Qualitative information about the solvent accessibility can be obtained from F-19 solvent PREs.
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    Boutureira, O.; Bernardes, G. J. L.; Fernández-González, M.; Anthony, D. C.; Davis, B. G. Angew. Chem., Int. Ed. 2012, 51, 1432– 1436
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    Selenenylsulfide-linked Homogeneous Glycopeptides and Glycoproteins: Synthesis of Human "Hepatic Se Metabolite A"
    Boutureira, Omar; Bernardes, Goncalo J. L.; Fernandez-Gonzalez, Marta; Anthony, Daniel C.; Davis, Benjamin G.
    Angewandte Chemie, International Edition (2012), 51 (6), 1432-1436, S1432/1-S1432/46CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The authors present the synthesis of selenenylsulfide-linked (glycosyl-SeS-Cys) glycopeptides and glycoproteins using a Cys-specific selenylation protocol of cysteine moiety in peptides and proteins, resp. The first synthesis and full characterization of human hepatic Se metabolite A, 5, is also reported.
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    Direct radiolabelling of proteins at cysteine using [18F]-fluorosugars
    Boutureira, Omar; Bernardes, Goncalo J. L.; D'Hooge, Francois; Davis, Benjamin G.
    Chemical Communications (Cambridge, United Kingdom) (2011), 47 (36), 10010-10012CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    A strategy for the site-specific attachment of 2-deoxy-2-fluorosugars to cysteine and dehydroalanine tagged proteins is reported. When combined with thionation of fluorosugars, such as the widely available 18F probe 2-deoxy-2-[18F]fluoroglucose ([18F]FDG), this methodol. allows fast and direct access to site-specific [18F]FDG-labeled proteins.
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    Enhancement of the Immunogenicity of Synthetic Carbohydrate Vaccines by Chemical Modifications of STn Antigen
    Yang, Fan; Zheng, Xiu-Jing; Huo, Chang-Xin; Wang, Yue; Zhang, Ye; Ye, Xin-Shan
    ACS Chemical Biology (2011), 6 (3), 252-259CODEN: ACBCCT; ISSN:1554-8929. (American Chemical Society)
    The abnormal glycans expressed on the surface of tumor cells, known as tumor-assocd. carbohydrate antigens, increase the chance to develop carbohydrate-based anticancer vaccines. However, carbohydrate antigens pose certain difficulties, and the major drawback is their weak immunogenicity. To tackle this problem, numerous structurally modified STn antigens were designed and synthesized in this work. These synthetic antigens were screened in vitro by using competitive ELISA method, and the antigens with pos. response were conjugated to the protein carrier for vaccination. The vaccination results on mice showed that some fluorine-contg. modifications on the STn antigen can significantly increase the anti-STn IgG titers and improve the ratios of anti-STn IgG/IgM. The antisera can recognize the tumor cells expressing the native STn antigen.
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    Boutureira, O.; D’Hooge, F.; Fernández-González, M.; Bernardes, G. J. L.; Sánchez-Navarro, M.; Koeppe, J. R.; Davis, B. G. Chem. Commun. 2010, 46, 8142– 8144
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    Fluoroglycoproteins: ready chemical site-selective incorporation of fluorosugars into proteins
    Boutureira, Omar; D'Hooge, Francois; Fernandez-Gonzalez, Marta; Bernardes, Goncalo J. L.; Sanchez-Navarro, Macarena; Koeppe, Julia R.; Davis, Benjamin G.
    Chemical Communications (Cambridge, United Kingdom) (2010), 46 (43), 8142-8144CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    A tag-and-modify strategy allows the practical synthesis of homogeneous fluorinated glyco-amino acids, peptides and proteins carrying a fluorine label in the sugar and allows access to first examples of directly radiolabeled ([18F]-glyco)proteins.
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    Fernández-González, M.; Boutureira, O.; Bernardes, G. J. L.; Chalker, J. M.; Young, M. A.; Errey, J. C.; Davis, B. G. Chem. Sci. 2010, 1, 709– 715
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    Site-selective chemoenzymatic construction of synthetic glycoproteins using endoglycosidases
    Fernandez-Gonzalez, Marta; Boutureira, Omar; Bernardes, Goncalo J. L.; Chalker, Justin M.; Young, Matthew A.; Errey, James C.; Davis, Benjamin G.
    Chemical Science (2010), 1 (6), 709-715CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
    Combined chem. tagging followed by Endo-A catalyzed elongation allows access to homogeneous, elaborated glycoproteins. A survey of different linkages and sugars demonstrated not only that unnatural linkages can be tolerated but they can provide insight into the scope of Endo-A transglycosylation activity. S-linked GlcNAc-glycoproteins are useful substrates for Endo-A extensions and display enhanced stability to hydrolysis at exposed sites. O-CH2-triazole-linked GlcNAc-glycoproteins derived from azidohomoalanine-tagged protein precursors were found to be optimal at sterically demanding sites.
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    Synthesis and Application of [18F]FDG-Maleimidehexyloxime ([18F]FDG-MHO): A [18F]FDG-Based Prosthetic Group for the Chemoselective 18F-Labeling of Peptides and Proteins
    Wuest, Frank; Berndt, Mathias; Bergmann, Ralf; van den Hoff, Joerg; Pietzsch, Jens
    Bioconjugate Chemistry (2008), 19 (6), 1202-1210CODEN: BCCHES; ISSN:1043-1802. (American Chemical Society)
    2-[18F]Fluoro-2-deoxy-D-glucose ([18F]FDG) as the most important PET radiotracer is available in almost every PET center. However, there are only very few examples using [18F]FDG as a building block for the synthesis of 18F-labeled compds. The present study describes the use of [18F]FDG as a building block for the synthesis of 18F-labeled peptides and proteins. [18F]FDG was converted into [18F]FDG-maleimidehexyloxime ([18F]FDG-MHO), a novel [18F]FDG-based prosthetic group for the mild and thiol group-specific 18F labeling of peptides and proteins. The reaction was performed at 100 °C for 15 min in a sealed vial contg. [18F]FDG and N-(6-aminoxy-hexyl)maleimide in 80% ethanol. [18F]FDG-MHO was obtained in 45-69% radiochem. yield (based upon [18F]FDG) after HPLC purifn. in a total synthesis time of 45 min. Chemoselective conjugation of [18F]FDG-MHO to thiol groups was investigated by the reaction with the tripeptide glutathione (GSH) and the single cysteine contg. protein annexin A5 (anxA5). Radiolabeled annexin A5 ([18F]FDG-MHO-anxA5) was obtained in 43-58% radiochem. yield (based upon [18F]FDG-MHO, n = 6), and [18F]FDG-MHO-anxA5 was used for a pilot small animal PET study to assess in vivo biodistribution and kinetics in a HT-29 murine xenograft model.
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    Adamo, R.; Nilo, A.; Castagner, B.; Boutureira, O.; Berti, F.; Bernardes, G. J. L. Chem. Sci. 2013, 4, 2995– 3008
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    Synthetically defined glycoprotein vaccines: current status and future directions
    Adamo, Roberto; Nilo, Alberto; Castagner, Bastien; Boutureira, Omar; Berti, Francesco; Bernardes, Goncalo J. L.
    Chemical Science (2013), 4 (8), 2995-3008CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
    A review. Primary examples in vaccine design have shown good levels of carbohydrate-specific antibody generation when raised using extd. or fully synthetic capsular polysaccharide glycans covalently coupled to a protein carrier. Herein, the authors cover recent clin. developments of carbohydrate-based vaccines and describe how novel cutting-edge methodol. for the total synthesis of oligosaccharides and for the precise placement of carbohydrates at pre-detd. sites within a protein may be used to further improve the safety and efficacy of glycovaccines.
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    Carbohydrate-Based Molecules for Molecular Imaging in Nuclear Medicine
    Ribeiro Morais, Goreti; Falconer, Robert A.; Santos, Isabel
    European Journal of Organic Chemistry (2013), 2013 (8), 1401-1414CODEN: EJOCFK; ISSN:1099-0690. (Wiley-VCH Verlag GmbH & Co. KGaA)
    This review covers published literature describing the synthesis of labeled carbohydrates for use in mol. imaging, with a particular focus on the use of nuclear techniques (PET, SPECT). Recent advances in the radiosynthesis of [18F]FDG (electrophilic vs. nucleophilic radiofluorinations), a PET radiotracer based on glucose and the most widely PET tracer currently in use for cancer and inflammatory disease diagnosis, is considered. The powerful impact of [18F]FDG in the clinic has prompted intensive research efforts into glucose-based radiotracers for PET and SPECT imaging. These achievements are also reviewed, along with the use of glycopeptides for nuclear mol. imaging. Finally, recent work on the radionuclide labeling of nucleosides and glycoconjugates is discussed.
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    Jacobson, Orit; Kiesewetter, Dale O.; Chen, Xiaoyuan
    Bioconjugate Chemistry (2015), 26 (1), 1-18CODEN: BCCHES; ISSN:1043-1802. (American Chemical Society)
    A review. Fluorine-18 is the most frequently used radioisotope in positron emission tomog. (PET) radiopharmaceuticals in both clin. and preclin. research. Its phys. and nuclear characteristics (97% β+ decay, 109.7 min half-life, 635 keV positron energy), along with high specific activity and ease of large scale prodn., make it an attractive nuclide for radiochem. labeling and mol. imaging. Versatile chem. including nucleophilic and electrophilic substitutions allows direct or indirect introduction of 18F into mols. of interest. The significant increase in 18F radiotracers for PET imaging accentuates the need for simple and efficient 18F-labeling procedures. In this review, we will describe the current radiosynthesis routes and strategies for 18F labeling of small mols. and biomols.
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    Ametamey, Simon M.; Honer, Michael; Schubiger, Pius August
    Chemical Reviews (Washington, DC, United States) (2008), 108 (5), 1501-1516CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
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    Tirotta, Ilaria; Dichiarante, Valentina; Pigliacelli, Claudia; Cavallo, Gabriella; Terraneo, Giancarlo; Bombelli, Francesca Baldelli; Metrangolo, Pierangelo; Resnati, Giuseppe
    Chemical Reviews (Washington, DC, United States) (2015), 115 (2), 1106-1129CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. This paper review the design of 19F magnetic resonance imaging agents and their application.
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    Chemical Reviews (Washington, DC, United States) (2015), 115 (5), 2174-2195CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. Transition metal-free and -mediated approaches are covered.
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    Carriere, D.; Meunier, S. J.; Tropper, F. D.; Cao, S.; Roy, R.
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    A review with 80 refs. summarizing results obtained over the past decade concerning the introduction of the fluorine atom into carbohydrate mols., either by nucleophilic substitution or electrophilic addn. reactions.
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  • Abstract

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    Scheme 1

    Scheme 1. General Strategies for the Preparation of 1-β-“Soft Nu”-2-deoxy-2-fluoroglycosides Using F+
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    Scheme 2

    Scheme 2. Phase-Transfer Catalyzed Reactions (PTC) for the Preparation of 7–12a
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    aGeneral conditions: 2-F-α-pyranosyl halide (1 equiv), Nu (2 equiv), TBAHS (2 equiv) in 5:1 EtOAc–1 M Na2CO3 aq (0.04 M), rt, from 1 h up to 7 days unless otherwise indicated.

    Determined by 19F NMR of the crude reaction mixture.

    2-F-α-galactosyl bromide 2b (1 equiv), Nu (2 equiv), TBAB (2 equiv) in 3:2 CH2Cl2–5% NaOH aq (0.02 M), rt, 14–22 h.

    2-F-α-galactosyl bromide 2b (2 equiv), estrone (1 equiv), 60% NaH in mineral oil (1.5 equiv) in dry 1,4-dioxane (0.08 M), rt, 24 h. Nu = nucleophile. TBAHS = tetrabutylammonium hydrogen sulfate. TBAB = tetrabutylammonium bromide.

    Scheme 3

    Scheme 3. Selective Chemical Protein Modification of Annexin V 13a
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    aGeneral conditions: Annexin V 13 (1 mg mL–1) (1 equiv), 2-F-sugar reagent 10a,b (250 equiv) in 20 mM Tris HCl buffer (pH 8.0) and 10% CH3CN, rt, 1 h.

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      Synthesis and biological evaluation of a novel MUC1 glycopeptide conjugate vaccine candidate comprising a 4'-deoxy-4'-fluoro-Thomsen-Friedenreich epitope
      Johannes, Manuel; Reindl, Maximilian; Gerlitzki, Bastian; Schmitt, Edgar; Hoffmann-Roeder, Anja
      Beilstein Journal of Organic Chemistry (2015), 11 (), 155-161/1-155-161/7, 7 pp.CODEN: BJOCBH; ISSN:1860-5397. (Beilstein-Institut zur Foerderung der Chemischen Wissenschaften)
      The development of selective anticancer vaccines that provide enhanced protection against tumor recurrence and metastasis has been the subject of intense research in the scientific community. The tumor-assocd. glycoprotein MUC1 represents a well-established target for cancer immunotherapy and has been used for the construction of various synthetic vaccine candidates. However, many of these vaccine prototypes suffer from an inherent low immunogenicity and are susceptible to rapid in vivo degrdn. To overcome these drawbacks, novel fluorinated MUC1 glycopeptide-BSA/TTox conjugate vaccines have been prepd. Immunization of mice with the 4'F-TF-MUC1-TTox conjugate resulted in strong immune responses overriding the natural tolerance against MUC1 and producing selective IgG antibodies that are cross-reactive with native MUC1 epitopes on MCF-7 human cancer cells.
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    2. 2
      Lamandé-Langle, S.; Collet, C.; Hensienne, R.; Vala, C.; Chrétien, F.; Chapleur, Y.; Mohamadi, A.; Lacolley, P.; Regnault, V. Bioorg. Med. Chem. 2014, 22, 6672– 6683
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      'Click' glycosylation of peptides through cysteine propargylation and CuAAC
      Lamande-Langle, Sandrine; Collet, Charlotte; Hensienne, Raphael; Vala, Christine; Chretien, Francoise; Chapleur, Yves; Mohamadi, Amel; Lacolley, Patrick; Regnault, Veronique
      Bioorganic & Medicinal Chemistry (2014), 22 (23), 6672-6683CODEN: BMECEP; ISSN:0968-0896. (Elsevier B.V.)
      'Click' glycosylation of cysteine-contg. peptides were carried out in good yield by copper(I)-catalyzed azide-alkyne cycloaddn. (CuAAC). For that peptides were functionalized though direct propargylation of the cysteine residue allowing their use in CuAAC with suitable free or protected azido sugars of gluco, manno and galacto configuration. Among these free and protected glycopeptides a series of 'glycoRGD' peptides were obtained and submitted to in vitro platelet aggregation tests, showing that the pseudoglycosylation of the adhesion sequence lowers the IC50 value and thus could improve the in vivo pharmacokinetic properties.
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    3. 3
      Dall’Angelo, S.; Zhang, Q.; Fleming, I. N.; Piras, M.; Schweiger, L. F.; O’Hagan, D.; Zanda, M. Org. Biomol. Chem. 2013, 11, 4551– 4558
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      Efficient bioconjugation of 5-fluoro-5-deoxy-ribose (FDR) to RGD peptides for positron emission tomography (PET) imaging of αvβ3 integrin receptor
      Dall'Angelo, Sergio; Zhang, Qingzhi; Fleming, Ian N.; Piras, Monica; Schweiger, Lutz F.; O'Hagan, David; Zanda, Matteo
      Organic & Biomolecular Chemistry (2013), 11 (27), 4551-4558CODEN: OBCRAK; ISSN:1477-0520. (Royal Society of Chemistry)
      The utility of 5-fluoro-5-deoxyribose (FDR) as an efficient bioconjugation agent for radiolabelling of the RGD peptides c(RGDfK) and c(RGDfC) is demonstrated. The bioconjugation is significantly superior to that achieved with 2-fluoro-2-deoxyglucose (FDG) and benefits from the location of the fluorine at C-5, and that ribose is a 5-membered ring sugar rather than a 6-membered ring. Both features favor ring opening to the aldehydic form of the sugar to promote smooth oxime ligation with aminooxy ether functionalised peptides. [18F]FDR was prepd. in this study by synthesis from fluoride-18 using an automated synthesis protocol adapting that used routinely for [18F]FDG. c(RGDfK) was functionalised with an aminooxyacetyl group (Aoa) via its lysine terminus, while c(RGDfC) was functionalised with an aminooxyhexylmaleimide (Ahm) through a cysteine-maleimide conjugation. Bioconjugation of [18F]FDR to c(RGDfC)-Ahm proved to be more efficient than c(RGDfK)-Aoa (92% vs. 65%). The unlabeled (19F) bioconjugates c(RGDfK)-Aoa-FDR and c(RGDfC)-Ahm-FDR were prepd. and their in vitro affinity to purified integrin αvβ3 was detd. c(RGDfK)-Aoa-FDR showed the greater affinity. Purified "hot" bioconjugates c(RGDfK)-Aoa-[18F]FDR and c(RGDfC)-Ahm-[18F]FDR were assayed by incubation with MCF7, LNCaP and PC3 cell lines. In both cases the conjugated RGD peptides showed selectivity for PC3 cells, which express αvβ3 integrin, with the c(RGDfK)-Aoa-[18F]FDR demonstrating better binding, consistent with its higher in vitro affinity. The study demonstrates that [18F]FDR is an efficient bioconjugation ligand for RGD bioactive peptides.
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      Lang, C.; Maschauer, S.; Hübner, H.; Gmeiner, P.; Prante, O. J. Med. Chem. 2013, 56, 9361– 9365
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      Synthesis and Evaluation of a 18F-Labeled Diarylpyrazole Glycoconjugate for the Imaging of NTS1-Positive Tumors
      Lang, Christopher; Maschauer, Simone; Huebner, Harald; Gmeiner, Peter; Prante, Olaf
      Journal of Medicinal Chemistry (2013), 56 (22), 9361-9365CODEN: JMCMAR; ISSN:0022-2623. (American Chemical Society)
      Aiming to image NTS1 over-expressing tumors, the diarylpyrazole glycoconjugate I, derived from the potent NTS1 antagonist, was synthesized taking advantage of the palladium-catalyzed aminocarbonylation reaction. The glycoconjugate I displayed excellent affinity and selectivity toward NTS1. Radio-synthesis proceeded straightforwardly, obtaining [18F]-I with excellent stability and highly beneficial bio-distribution in vivo as demonstrated by PET imaging in HT29 tumor-bearing nude mice. Thus, the tracer [18F]-I represents a highly promising candidate for PET imaging of NTS1-pos. tumors.
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      Li, X.-G.; Dall’Angelo, S.; Schweiger, L. F.; Zanda, M.; O’Hagan, D. Chem. Commun. 2012, 48, 5247– 5249
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      [18F]-5-Fluoro-5-deoxyribose, an efficient peptide bioconjugation ligand for positron emission tomography (PET) imaging
      Li, Xiang-Guo; Dall'Angelo, Sergio; Schweiger, Lutz F.; Zanda, Matteo; O'Hagan, David
      Chemical Communications (Cambridge, United Kingdom) (2012), 48 (43), 5247-5249CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      [18F]-5-Fluoro-5-deoxyribose ([18F]-FDR) conjugates much more rapidly than [18F]-FDG under mild reaction conditions to peptides and offers new prospects for mild and rapid bioconjugation for fluorine-18 labeling in PET imaging.
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      Maschauer, S.; Einsiedel, J.; Haubner, R.; Hocke, C.; Ocker, M.; Hübner, H.; Kuwert, T.; Gmeiner, P.; Prante, O. Angew. Chem., Int. Ed. 2010, 49, 976– 979
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      Labeling and Glycosylation of Peptides Using Click Chemistry: A General Approach to 18F-Glycopeptides as Effective Imaging Probes for Positron Emission Tomography
      Maschauer, Simone; Einsiedel, Juergen; Haubner, Roland; Hocke, Carsten; Ocker, Matthias; Huebner, Harald; Kuwert, Torsten; Gmeiner, Peter; Prante, Olaf
      Angewandte Chemie, International Edition (2010), 49 (5), 976-979, S976/1-S976/18CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Click chem. was used for 18F-labeling of glycopeptides for potential use as PET imaging agents.
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      Hoffmann-Röder, A.; Kaiser, A.; Wagner, S.; Gaidzik, N.; Kowalczyk, D.; Westerlind, U.; Gerlitzki, B.; Schmitt, E.; Kunz, H. Angew. Chem., Int. Ed. 2010, 49, 8498– 8503
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      Synthetic antitumor vaccines from tetanus toxoid conjugates of MUC1 glycopeptides with the Thomsen-Friedenreich antigen and a fluorine-substituted analogue
      Hoffmann-Roder Anja; Kaiser Anton; Wagner Sarah; Gaidzik Nikola; Kowalczyk Danuta; Westerlind Ulrika; Gerlitzki Bastian; Schmitt Edgar; Kunz Horst
      Angewandte Chemie (International ed. in English) (2010), 49 (45), 8498-503 ISSN:.
      There is no expanded citation for this reference.
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      Wuest, F.; Hultsch, C.; Berndt, M.; Bergmann, R. Bioorg. Med. Chem. Lett. 2009, 19, 5426– 5428
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      Direct labelling of peptides with 2-[18F]fluoro-2-deoxy-D-glucose ([18F]FDG)
      Wuest, Frank; Hultsch, Christina; Berndt, Mathias; Bergmann, Ralf
      Bioorganic & Medicinal Chemistry Letters (2009), 19 (18), 5426-5428CODEN: BMCLE8; ISSN:0960-894X. (Elsevier B.V.)
      The study describes the use of [18F]FDG as 18F building block for the direct labeling of various aminooxy-functionalised peptides via chemoselective oxime formation.
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      Prante, O.; Einsiedel, J.; Haubner, R.; Gmeiner, P.; Wester, H.-J.; Kuwert, T.; Maschauer, S. Bioconjugate Chem. 2007, 18, 254– 262
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      3,4,6-Tri-O-acetyl-2-deoxy-2-[18F]fluoroglucopyranosyl Phenylthiosulfonate: A Thiol-Reactive Agent for the Chemoselective 18F-Glycosylation of Peptides
      Prante, Olaf; Einsiedel, Juergen; Haubner, Roland; Gmeiner, Peter; Wester, Hans-Juergen; Kuwert, Torsten; Maschauer, Simone
      Bioconjugate Chemistry (2007), 18 (1), 254-262CODEN: BCCHES; ISSN:1043-1802. (American Chemical Society)
      3,4,5-Tri-O-acetyl-2-[18F]fluoro-2-deoxy-D-glucopyranosyl 1-phenylthiosulfonate (I) was developed as a thiol-reactive labeling reagent for the site-specific 18F-glycosylation of peptides. Starting from 1,3,4,6-tetra-O-acetyl-2-deoxy-2-[18F]fluoroglucopyranose, a three-step radiochem. pathway was investigated and optimized, and I was obtained in a radiochem. yield of about 33% in 90 min (decay-cor. and based on starting [18F]fluoride). I was reacted with the model pentapeptide CAKAY, providing chemoselectivity and excellent conjugation yields of >90% under mild reaction conditions. The optimized method was adopted to the 18F-glycosylation of the αvβ3-affine peptide cyclo(RGDfC), achieving high conjugation yields (95%, decay-cor.). The αvβ3 binding affinity of the glycosylated cyclo(RGDfC) remained uninfluenced as detd. by competition binding studies vs. 125I-echistatin using both isolated αvβ3 and human umbilical vein endothelial cells (Ki = 68 ± 10 nM (αvβ3) vs. Ki = 77 ± 4 nM (HUVEC)). The whole radiosynthetic procedure, including the prepn. of I, peptide ligation, and final HPLC purifn., provided a decay-uncorrected radiochem. yield of 13% after a total synthesis time of 130 min. I can be used to prep. 18F-labeled bioactive S-glycopeptides for studying their pharmacokinetics in vivo by positron emission tomog. (PET).
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      Huo, C.-X.; Zheng, X.-J.; Xiao, A.; Liu, C.-C.; Sun, S.; Lv, Z.; Ye, X.-S. Org. Biomol. Chem. 2015, 13, 3677– 3690
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      Synthetic and immunological studies of N-acyl modified S-linked STn derivatives as anticancer vaccine candidates
      Huo, Chang-Xin; Zheng, Xiu-Jing; Xiao, An; Liu, Chang-Cheng; Sun, Shuang; Lv, Zhuo; Ye, Xin-Shan
      Organic & Biomolecular Chemistry (2015), 13 (12), 3677-3690CODEN: OBCRAK; ISSN:1477-0520. (Royal Society of Chemistry)
      It is well known that tumor cells express some aberrant glycans, termed tumor-assocd. carbohydrate antigens (TACAs). TACAs are good targets for the development of carbohydrate-based anticancer vaccines. However, one of the major problems is that carbohydrate antigens possess a weak immunogenicity. To tackle this problem, a no. of unnatural N-modified S-linked STn analogs were designed and prepd. Reaction of the modified STn disaccharides with bifunctional adipic acid p-nitrophenyl diester provided the corresponding activated esters, which was followed by the conjugation with keyhole limpet hemocyanin (KLH), affording the corresponding protein conjugates. The immunol. properties of these glycoconjugates were evaluated in a mouse model. The results showed that the modified glycoconjugates stimulated the prodn. of IgG antibodies that are capable of recognizing the naturally occurring STn antigen, helping the discovery of carbohydrate-based anticancer vaccine candidates.
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    11. 11
      Lee, H.-Y.; Chen, C.-Y.; Tsai, T.-I.; Li, S.-T.; Lin, K.-H.; Cheng, Y.-Y.; Ren, C.-T.; Cheng, T.-J. R.; Wu, C.-Y.; Wong, C.-H. J. Am. Chem. Soc. 2014, 136, 16844– 16853
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      Immunogenicity study of Globo H analogues with modification at the reducing or nonreducing end of the tumor antigen
      Lee, Hsin-Yu; Chen, Chien-Yu; Tsai, Tsung-I.; Li, Shiou-Ting; Lin, Kun-Hsien; Cheng, Yang-Yu; Ren, Chien-Tai; Cheng, Ting-Jen R.; Wu, Chung-Yi; Wong, Chi-Huey
      Journal of the American Chemical Society (2014), 136 (48), 16844-16853CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Globo H-based therapeutic cancer vaccines have been tested in clin. trials for the treatment of late stage breast, ovarian, and prostate cancers. In this study, we explored Globo H analog antigens with an attempt to enhance the antigenic properties in vaccine design. The Globo H analogs with modification at the reducing or nonreducing end were synthesized using chemoenzymic methods, and these modified Globo H antigens were then conjugated with the carrier protein diphtheria toxoid cross-reactive material (CRM) 197 (DT), and combined with a glycolipid C34 as an adjuvant designed to induce a class switch to form the vaccine candidates. After Balb/c mice injection, the immune response was studied by a glycan array and the results showed that modification at the C-6 position of reducing end glucose of Globo H with the fluoro, azido, or Ph group elicited IgG antibody response to specifically recognize Globo H (GH) and the GH-related epitopes, stage-specific embryonic antigen 3 (SSEA3) (also called Gb5) and stage-specific embryonic antigen 4 (SSEA4). However, only the modification of Globo H with the azido group at the C-6 position of the nonreducing end fucose could elicit a strong IgG immune response. Moreover, the antibodies induced by these vaccines were shown to recognize GH expressing tumor cells (MCF-7) and mediate the complement-dependent cell cytotoxicity against tumor cells. Our data suggest a new potential approach to cancer vaccine development.
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      Orwenyo, J.; Huang, W.; Wang, L. X. Bioorg. Med. Chem. 2013, 21, 4768– 4777
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      Chemoenzymatic synthesis and lectin recognition of a selectively fluorinated glycoprotein
      Orwenyo, Jared; Huang, Wei; Wang, Lai-Xi
      Bioorganic & Medicinal Chemistry (2013), 21 (16), 4768-4777CODEN: BMECEP; ISSN:0968-0896. (Elsevier B.V.)
      A chemoenzymic glycosylation remodeling method for the synthesis of selectively fluorinated glycoproteins is described. The method consists of chem. synthesis of a fluoroglycan oxazoline and its use as donor substrate for endoglycosidase (ENGase)-catalyzed transglycosylation to a GlcNAc-protein to form a homogeneous fluoroglycoprotein. The approach was exemplified by the synthesis of fluorinated glycoforms of RNase B. An interesting finding was that fluorination at the C-6 of the 6-branched mannose moiety in the Man3GlcNAc core resulted in significantly enhanced reactivity of the substrate in enzymic transglycosylation. A structural anal. suggests that the enhancement in reactivity may come from favorable hydrophobic interactions between the fluorine and a tyrosine residue in the catalytic site of the enzyme (Endo-A). SPR anal. of the binding of the fluorinated glycoproteins with lectin Con A (con A) revealed the importance of the 6-hydroxyl group on the α-1,6-branched mannose moiety in con A recognition. The present study establishes a facile method for prepn. of selectively fluorinated glycoproteins that can serve as valuable probes for elucidating specific carbohydrate-protein interactions.
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      Fröhlich, R. F. G.; Schrank, E.; Zangger, K. Carbohydr. Res. 2012, 361, 100– 104
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      2,2,2-Trifluoroethyl 6-thio-β-D-glucopyranoside as a selective tag for cysteines in proteins
      Frohlich Richard F G; Schrank Evelyne; Zangger Klaus
      Carbohydrate research (2012), 361 (), 100-4 ISSN:.
      A synthetic route to a trifluoromethyl and thiol containing glucose derivative (2,2,2-trifluoroethyl 6-thio-β-D-glucopyranoside) is presented, which is based on microwave-assisted Fischer glycosylation under increased pressure. This water-soluble, neutral thiol-compound can be used to selectively introduce a fluorine probe for (19)F NMR spectroscopy on cysteines in proteins. It can be attached under mild conditions in an aqueous environment without the risk of denaturing the protein. This tag has been applied to determine the redox-state of two cysteine residues in a bacterial transcription activator. Qualitative information about the solvent accessibility can be obtained from F-19 solvent PREs.
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      Boutureira, O.; Bernardes, G. J. L.; Fernández-González, M.; Anthony, D. C.; Davis, B. G. Angew. Chem., Int. Ed. 2012, 51, 1432– 1436
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      Selenenylsulfide-linked Homogeneous Glycopeptides and Glycoproteins: Synthesis of Human "Hepatic Se Metabolite A"
      Boutureira, Omar; Bernardes, Goncalo J. L.; Fernandez-Gonzalez, Marta; Anthony, Daniel C.; Davis, Benjamin G.
      Angewandte Chemie, International Edition (2012), 51 (6), 1432-1436, S1432/1-S1432/46CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The authors present the synthesis of selenenylsulfide-linked (glycosyl-SeS-Cys) glycopeptides and glycoproteins using a Cys-specific selenylation protocol of cysteine moiety in peptides and proteins, resp. The first synthesis and full characterization of human hepatic Se metabolite A, 5, is also reported.
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      Boutureira, O.; Bernardes, G. J. L.; D’Hooge, F.; Davis, B. G. Chem. Commun. 2011, 47, 10010– 10012
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      Direct radiolabelling of proteins at cysteine using [18F]-fluorosugars
      Boutureira, Omar; Bernardes, Goncalo J. L.; D'Hooge, Francois; Davis, Benjamin G.
      Chemical Communications (Cambridge, United Kingdom) (2011), 47 (36), 10010-10012CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      A strategy for the site-specific attachment of 2-deoxy-2-fluorosugars to cysteine and dehydroalanine tagged proteins is reported. When combined with thionation of fluorosugars, such as the widely available 18F probe 2-deoxy-2-[18F]fluoroglucose ([18F]FDG), this methodol. allows fast and direct access to site-specific [18F]FDG-labeled proteins.
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      Yang, F.; Zheng, X.-J.; Huo, C.-X.; Wang, Y.; Zhang, Y.; Ye, X.-S. ACS Chem. Biol. 2011, 6, 252– 259
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      16
      Enhancement of the Immunogenicity of Synthetic Carbohydrate Vaccines by Chemical Modifications of STn Antigen
      Yang, Fan; Zheng, Xiu-Jing; Huo, Chang-Xin; Wang, Yue; Zhang, Ye; Ye, Xin-Shan
      ACS Chemical Biology (2011), 6 (3), 252-259CODEN: ACBCCT; ISSN:1554-8929. (American Chemical Society)
      The abnormal glycans expressed on the surface of tumor cells, known as tumor-assocd. carbohydrate antigens, increase the chance to develop carbohydrate-based anticancer vaccines. However, carbohydrate antigens pose certain difficulties, and the major drawback is their weak immunogenicity. To tackle this problem, numerous structurally modified STn antigens were designed and synthesized in this work. These synthetic antigens were screened in vitro by using competitive ELISA method, and the antigens with pos. response were conjugated to the protein carrier for vaccination. The vaccination results on mice showed that some fluorine-contg. modifications on the STn antigen can significantly increase the anti-STn IgG titers and improve the ratios of anti-STn IgG/IgM. The antisera can recognize the tumor cells expressing the native STn antigen.
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      Boutureira, O.; D’Hooge, F.; Fernández-González, M.; Bernardes, G. J. L.; Sánchez-Navarro, M.; Koeppe, J. R.; Davis, B. G. Chem. Commun. 2010, 46, 8142– 8144
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      Fluoroglycoproteins: ready chemical site-selective incorporation of fluorosugars into proteins
      Boutureira, Omar; D'Hooge, Francois; Fernandez-Gonzalez, Marta; Bernardes, Goncalo J. L.; Sanchez-Navarro, Macarena; Koeppe, Julia R.; Davis, Benjamin G.
      Chemical Communications (Cambridge, United Kingdom) (2010), 46 (43), 8142-8144CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      A tag-and-modify strategy allows the practical synthesis of homogeneous fluorinated glyco-amino acids, peptides and proteins carrying a fluorine label in the sugar and allows access to first examples of directly radiolabeled ([18F]-glyco)proteins.
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      Fernández-González, M.; Boutureira, O.; Bernardes, G. J. L.; Chalker, J. M.; Young, M. A.; Errey, J. C.; Davis, B. G. Chem. Sci. 2010, 1, 709– 715
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      Site-selective chemoenzymatic construction of synthetic glycoproteins using endoglycosidases
      Fernandez-Gonzalez, Marta; Boutureira, Omar; Bernardes, Goncalo J. L.; Chalker, Justin M.; Young, Matthew A.; Errey, James C.; Davis, Benjamin G.
      Chemical Science (2010), 1 (6), 709-715CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
      Combined chem. tagging followed by Endo-A catalyzed elongation allows access to homogeneous, elaborated glycoproteins. A survey of different linkages and sugars demonstrated not only that unnatural linkages can be tolerated but they can provide insight into the scope of Endo-A transglycosylation activity. S-linked GlcNAc-glycoproteins are useful substrates for Endo-A extensions and display enhanced stability to hydrolysis at exposed sites. O-CH2-triazole-linked GlcNAc-glycoproteins derived from azidohomoalanine-tagged protein precursors were found to be optimal at sterically demanding sites.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtl2nsLnE&md5=613c61342fa65cd1273e79866d7bead4
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      Synthesis and Application of [18F]FDG-Maleimidehexyloxime ([18F]FDG-MHO): A [18F]FDG-Based Prosthetic Group for the Chemoselective 18F-Labeling of Peptides and Proteins
      Wuest, Frank; Berndt, Mathias; Bergmann, Ralf; van den Hoff, Joerg; Pietzsch, Jens
      Bioconjugate Chemistry (2008), 19 (6), 1202-1210CODEN: BCCHES; ISSN:1043-1802. (American Chemical Society)
      2-[18F]Fluoro-2-deoxy-D-glucose ([18F]FDG) as the most important PET radiotracer is available in almost every PET center. However, there are only very few examples using [18F]FDG as a building block for the synthesis of 18F-labeled compds. The present study describes the use of [18F]FDG as a building block for the synthesis of 18F-labeled peptides and proteins. [18F]FDG was converted into [18F]FDG-maleimidehexyloxime ([18F]FDG-MHO), a novel [18F]FDG-based prosthetic group for the mild and thiol group-specific 18F labeling of peptides and proteins. The reaction was performed at 100 °C for 15 min in a sealed vial contg. [18F]FDG and N-(6-aminoxy-hexyl)maleimide in 80% ethanol. [18F]FDG-MHO was obtained in 45-69% radiochem. yield (based upon [18F]FDG) after HPLC purifn. in a total synthesis time of 45 min. Chemoselective conjugation of [18F]FDG-MHO to thiol groups was investigated by the reaction with the tripeptide glutathione (GSH) and the single cysteine contg. protein annexin A5 (anxA5). Radiolabeled annexin A5 ([18F]FDG-MHO-anxA5) was obtained in 43-58% radiochem. yield (based upon [18F]FDG-MHO, n = 6), and [18F]FDG-MHO-anxA5 was used for a pilot small animal PET study to assess in vivo biodistribution and kinetics in a HT-29 murine xenograft model.
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      Chemical Science (2013), 4 (8), 2995-3008CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
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      A review. Fluorine-18 is the most frequently used radioisotope in positron emission tomog. (PET) radiopharmaceuticals in both clin. and preclin. research. Its phys. and nuclear characteristics (97% β+ decay, 109.7 min half-life, 635 keV positron energy), along with high specific activity and ease of large scale prodn., make it an attractive nuclide for radiochem. labeling and mol. imaging. Versatile chem. including nucleophilic and electrophilic substitutions allows direct or indirect introduction of 18F into mols. of interest. The significant increase in 18F radiotracers for PET imaging accentuates the need for simple and efficient 18F-labeling procedures. In this review, we will describe the current radiosynthesis routes and strategies for 18F labeling of small mols. and biomols.
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      A review. Transition metal-free and -mediated approaches are covered.
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      The synthesis of the TXA2/PGH2 receptor antagonist I from the known chiral intermediate (-)-II is described. The crit. reaction is the inversion of C-5 in III by an intramol. cyclization reaction induced by nucleophilic reagents. The key intermediate IV was prepd. in 26.5% yield in five steps. Diastereoselectivity is high in all but one of the steps. I is a receptor antagonist devoid of agonist activity, which binds to the receptor with nanomolar affinity. These findings lend support to the view of single TXA2/PGH2 receptor.
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      Reaction of Me3SiI with penta-O-acetylhexopyranoses or tetra-O-acetyl-2-deoxyhexopyranoses gave the corresponding glycosyl iodides and 2-deoxyglycosyl iodides, resp. Me glycosides reacted similarly, and lactose octaacetate gave hepta-O-acetyl-α-D-lactosyl iodide. Similar reactions with Me3SiBr gave the corresponding glycosyl bromides. By opening of epoxides with Me3SiI in the case of sterically fixed saccharide oxiranes the trans-diaxial, and in the case of more flexible derivs. predominantly the trans-diequatorial iodohydrins were obtained.
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      The original 1967 Richardson-Hough rules for predicting SN2 displacement viability in carbohydrate sulfonate derivs. with external nucleophiles have now been updated. Not only do the original rules still hold, but the newly updated rules rationalize why O-triflates (trifluoromethanesulfonate esters) frequently allow many seemingly "disallowed" pyranosidic nucleophilic substitutions to proceed. The new guidelines, which are based on three decades of exptl. evidence, allow the feasibility of many pyranosidic O-triflate SN2 displacements to be gauged beforehand.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsFCjt7nF&md5=9b508c2db4ef5695f3d0cd03fb8347bf
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtVygsbvL&md5=563471996f250299c82e6bacc0f7d741

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