ACS Publications. Most Trusted. Most Cited. Most Read

OR SEARCH CITATIONS

My Activity
Publications
CONTENT TYPES

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Org. Chem. 2000, 65, 20, 6601-6612
RETURN TO ISSUEPREVArticleNEXT

On the Behavior of α,β-Unsaturated Thioaldehydes and Thioketones in the Diels−Alder Reaction

View Author Information
Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, and Department of Chemistry and Chemical Engineering, Faculty of Engineering, Kanazawa University, 2-40-20 Kodatsuno, Kanazawa 920-8667, Japan
Cite this: J. Org. Chem. 2000, 65, 20, 6601–6612
Publication Date (Web):August 31, 2000
https://doi.org/10.1021/jo000740q
Copyright © 2000 American Chemical Society
Request reuse permissions

    Article Views

    618

    Altmetric

    -

    Citations

    30
    LEARN ABOUT THESE METRICS
    Read OnlinePDF (368 KB)
    Get e-Alerts
    Supporting Info (1)»
    SUBJECTS:

    Abstract

    Abstract Image

    α,β-Unsaturated thioaldehydes and thioketones, R1CHCH−C(S)R2, are prepared in situ by the reaction between the corresponding carbonyl compounds and bis(dimethylaluminum) sulfide. These compounds undergo [4 + 2] self-dimerization reactions in which one molecule serves as the heterodiene component and the other as the dienophile to afford different types of dimeric products depending on the R1 and R2:  1,2-dithiin and 1,3-dithiin (R1 = R2 = H), 1,2-dithiin (R1 = Ph, R2 = H, CH3), or dihydrothiopyran (R1 = R2 = Ph). These differences in selectivity are explained on the basis of the relative energies evaluated by molecular orbital (MO) calculations at the DFT (density functional theory) level. The calculations show that in the dimerization reaction of thioacrolein (I), the head-to-tail (S−C−S bonded) dimers are kinetically more stable by about 5 kcal/mol but slightly thermodynamically unstable by about 2 kcal/mol than the head-to-head (S−S bonded) dimers. The calculations on thiocinnamaldehyde (IV) indicate that the dimerization reactions of phenyl-substituted α,β-unsaturated thioaldehydes and thioketones are almost equally controlled by thermodynamic and kinetic factors. These unsaturated thiocarbonyl compounds also function as heterodienes (CC−CS) in the cycloaddition reaction with norbornadiene and as dienophiles (CS) in the reaction with cyclopentadiene.

    *

    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

    †

     Texas A&M University.

    ‡

     Present address:  Research & Development Department, Cosmetics Division, Tokiwa Corp., 1-18-11 Shinden, Adachi-Ku, Tokyo 123-0865, Japan.

    §

     Present address:  Pacific Northwest National Laboratory, Richland, Washington 99352.

    ‖

     Kanazawa University.

    Supporting Information Available

    ARTICLE SECTIONS
    Jump To

    1H and 13C NMR spectra of 4, 6, 8, 10, 11, 12, 14, and 15. Packing diagram, tables of crystal data and structure refinement, atomic coordinates and isotropic and anisotropic displacement parameters, and bond distances and angles for 6. This material is available free of charge via the Internet at http://pubs.acs.org.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 30 publications.

    1. Ting Yan, Le Wu, Litao Wang, Feng Fu, Tao Fang. Desulfurization of Sulfur-Containing Compounds in Heavy Oil in the Presence of Supercritical Methanol. Energy & Fuels 2020, 34 (3) , 2958-2968. https://doi.org/10.1021/acs.energyfuels.9b04148
    2. Vandana Jaiswal, Biplab Mondal, Kuldeep Singh, Dinabandhu Das, Jaideep Saha. [3 + 2]-Annulation of Azaoxyallyl Cations and Thiocarbonyls for the Assembly of Thiazolidin-4-ones. Organic Letters 2019, 21 (15) , 5848-5852. https://doi.org/10.1021/acs.orglett.9b01933
    3. Luis R. Domingo, Raúl Pérez-Ruiz, Juan E. Argüello and Miguel A. Miranda . DFT Study on the Molecular Mechanism of the [4 + 2] Cycloaddition between Thiobenzophenone and Arylalkenes via Radical Cations. The Journal of Physical Chemistry A 2009, 113 (19) , 5718-5722. https://doi.org/10.1021/jp900486e
    4. Chi-Hsiang Chuang and, Min-Hsiung Lien. Ab Initio Study on the Effects of the Substituent and the Functional Group on the Isomerization of H3CC(X)Y and H2C(X)CHY (Y = SiH2, PH, S; X = H, CH3, NH2, OH, F). The Journal of Physical Chemistry A 2004, 108 (10) , 1790-1798. https://doi.org/10.1021/jp0371332
    5. Ekaterina A. Merkulova, Aleksey V. Kolobov, Konstantin A. Lyssenko, Valentine G. Nenajdenko. Diene-transmissive hetero-Diels–Alder reaction of distyryl thioketone. Mendeleev Communications 2022, 32 (3) , 384-385. https://doi.org/10.1016/j.mencom.2022.05.031
    6. Navjeet Kaur. S-Heterocycle Synthesis. 2022, 175-214. https://doi.org/10.1007/978-981-16-4655-3_6
    7. Taichi Yoneda, Naoto Kojima, Takahiro Matsumoto, Daisuke Imahori, Tomoe Ohta, Tatsusada Yoshida, Tetsushi Watanabe, Hisashi Matsuda, Seikou Nakamura. Construction of sulfur-containing compounds with anti-cancer stem cell activity using thioacrolein derived from garlic based on nature-inspired scaffolds. Organic & Biomolecular Chemistry 2021, 20 (1) , 196-207. https://doi.org/10.1039/D1OB01992A
    8. Philipp Buday, Phillip Seeber, Clara Zens, Hassan Abul‐Futouh, Helmar Görls, Stefanie Gräfe, Piotr Matczak, Stephan Kupfer, Wolfgang Weigand, Grzegorz Mloston. Iron(0)‐Mediated Stereoselective (3+2)‐Cycloaddition of Thiochalcones via a Diradical Intermediate. Chemistry – A European Journal 2020, 26 (50) , 11412-11416. https://doi.org/10.1002/chem.202001412
    9. Grzegorz Mlostoń, Katarzyna Urbaniak, Marcin Jasiński, Ernst‐Ulrich Würthwein, Heinz Heimgartner, Reinhold Zimmer, Hans‐Ulrich Reissig. The [4+2]‐Cycloaddition of α‐Nitrosoalkenes with Thiochalcones as a Prototype of Periselective Hetero‐Diels–Alder Reactions—Experimental and Computational Studies. Chemistry – A European Journal 2020, 26 (1) , 237-248. https://doi.org/10.1002/chem.201903385
    10. Toshiaki Murai. The Construction and Application of C=S Bonds. Topics in Current Chemistry 2018, 376 (4) https://doi.org/10.1007/s41061-018-0209-0
    11. Laura Scheffler, Yvonne Sauermann, Gina Zeh, Katharina Hauf, Anja Heinlein, Constanze Sharapa, Andrea Buettner. Detection of Volatile Metabolites of Garlic in Human Breast Milk. Metabolites 2016, 6 (2) , 18. https://doi.org/10.3390/metabo6020018
    12. Catherine H. Kaschula, Roger Hunter. Synthesis and Structure–Activity Relations in Allylsulfide and Isothiocyanate Compounds From Garlic and Broccoli Against In Vitro Cancer Cell Growth. 2016, 1-43. https://doi.org/10.1016/B978-0-444-63749-9.00001-3
    13. Nidhi Sogani, Pragya Sinha, Raj K. Bansal. Hetero-Diels–Alder reaction of aromatic aldehydes catalyzed by titanium tetrachloride: computational and experimental results. Tetrahedron 2014, 70 (3) , 735-741. https://doi.org/10.1016/j.tet.2013.11.077
    14. E. Kleinpeter, M. Sefkow. 1,3-Dioxins, Oxathiins, Dithiins, and their Benzo Derivatives. 2008, 739-856. https://doi.org/10.1016/B978-008044992-0.00711-2
    15. Masahito Segi, Katsuhiko Kawaai, Mitsunori Honda, Shuhei Fujinami. Stereoselective hetero Diels–Alder reaction of selenoaldehydes with pentavalent phosphole chalcogenides. Tetrahedron Letters 2007, 48 (19) , 3349-3354. https://doi.org/10.1016/j.tetlet.2007.03.079
    16. Daniel H. Egli, Anthony Linden, Heinz Heimgartner. Reactions of Thioketones Possessing a Conjugated CC Bond with Diazo Compounds. Helvetica Chimica Acta 2006, 89 (12) , 3041-3055. https://doi.org/10.1002/hlca.200690274
    17. Alejandro M. Granados, Alejandro M. Fracaroli, Jeronimo Kreiker, Rita H. de Rossi. Disconnection of the organic moiety in chromium and tungsten complexes [(dithiin)M(CO) 5 ]. Journal of Physical Organic Chemistry 2006, 19 (12) , 823-828. https://doi.org/10.1002/poc.1044
    18. Wolfdieter A. Schenk, Thomas Beucke, Nicolai Burzlaff, Matthias Klüglein, Marco Stemmler. Ruthenium Complexes of Thiocinnamaldehydes: Synthesis, Structure, and [4+2]-Cycloaddition Reactions. Chemistry - A European Journal 2006, 12 (18) , 4821-4834. https://doi.org/10.1002/chem.200501430
    19. Raj K. Bansal, Neelima Gupta, Surendra K. Kumawat. Origin of the stereo- and regioselectivities in the Diels–Alder reactions of azaphospholes: a DFT investigation. Tetrahedron 2006, 62 (7) , 1548-1556. https://doi.org/10.1016/j.tet.2005.11.009
    20. Raj K. Bansal, Neelima Gupta, Surendra K. Kumawat, Raakhi Gupta. Diels–Alder reactions of 5,6-dihydrothiazolo[3,2-d][1,4,2]diazaphospholes: A DFT investigation. Heteroatom Chemistry 2006, 17 (5) , 402-410. https://doi.org/10.1002/hc.20196
    21. Alessandro Degl’Innocenti, Antonella Capperucci, Irene Malesci, Giulio Castagnoli. Unusual chemical behaviour of silylated 1,2-dithiins under Lewis acid conditions. Tetrahedron Letters 2005, 46 (28) , 4711-4713. https://doi.org/10.1016/j.tetlet.2005.05.048
    22. Antonella Capperucci, Alessandro Degl'Innocenti, Tiziano Nocentini, Giulio Castagnoli, Irene Malesci, Arianna Cerreti. HMDST as Useful Tool in Organic Synthesis: A Further Step in the Delivery of Sulfur Functionalities. Phosphorus, Sulfur, and Silicon and the Related Elements 2005, 180 (5-6) , 1247-1251. https://doi.org/10.1080/10426500590911430
    23. N.J. Cooper. Thioaldehydes and Thioketones. 2005, 355-396. https://doi.org/10.1016/B0-08-044655-8/00053-2
    24. Tobias Persson, Thomas H. Hansen, Thomas B. Rasmussen, Mette E. Skindersø, Michael Givskov, John Nielsen. Rational design and synthesis of new quorum-sensing inhibitors derived from acylated homoserine lactones and natural products from garlic. Org. Biomol. Chem. 2005, 3 (2) , 253-262. https://doi.org/10.1039/B415761C
    25. Edward R. Biehl, Ramadas Sathunuru. Facile Synthesis of 5-Acyl-2-amino- 1,3-thiazole by the Reaction of Thiaazadienes with a-Halo Ketones. HETEROCYCLES 2004, 63 (12) , 2805. https://doi.org/10.3987/COM-04-10231
    26. Antonella Capperucci, Alessandro Degl'Innocenti, Tiziano Nocentini, Simona Biondi, Francesca Dini. α,β-Unsaturated thioacylsilanes as efficient dienes in hetero Diels–Alder reactions. Journal of Organometallic Chemistry 2003, 686 (1-2) , 363-367. https://doi.org/10.1016/S0022-328X(03)00615-6
    27. Antonella Capperucci, Alessandro Degl'Innocenti, Simona Biondi, Tiziano Nocentini, Giuseppe Rinaudo. An easy access to α,β-unsaturated thioacylsilanes: a useful route to silylated 1,2-dithiins. Tetrahedron Letters 2003, 44 (14) , 2831-2835. https://doi.org/10.1016/S0040-4039(03)00445-3
    28. Kentaro Okuma. Recent Studies on the Reactions of Thioaldehydes and Thioketones. Sulfur reports 2002, 23 (2) , 209-241. https://doi.org/10.1080/01961770208047971
    29. Guang Ming Li, Shuqiang Niu, Masahito Segi, Koichiro Tanaka, Tadashi Nakajima, Ralph A. Zingaro, Joseph H. Reibenspies, Michael B. Hall. ChemInform Abstract: On the Behavior of α,β-Unsaturated Thioaldehydes and Thioketones in the Diels-Alder Reaction.. ChemInform 2001, 32 (7) , no-no. https://doi.org/10.1002/chin.200107039
    30. John D. Hepworth, B. Mark Heron. Six-Membered Ring Systems: With O and/or S Atoms. 2001, 317-339. https://doi.org/10.1016/S0959-6380(01)80017-9
    Download PDF

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect