An Improved Synthesis of Vinyl- and β-Iodovinyl Sulfones by a Molecular Iodine-Mediated One-Pot Iodosulfonation-Dehydroiodination Reaction

REFERENCES

• For recent works, see (a) Honma , M. ; Takeda , H. ; Takano , M. ; Nakada , M. Development of catalytic asymmetric intramolecular cyclopropanation of α -diazo-β-keto sulfones and applications to natural product synthesis. Synlett 2009, 1695–1712; (b) Back , T. G. Design and synthesis of some biologically interesting natural and unnatural products based on organosulfur and selenium chemistry. Can. J. Chem. 2009, 87, 1657–1674; (c) Martinelli , F. ; Palmieri , A. ; Petrini , M. Arylsulfonyl group: Activating properties and recent synthetic applications. Phosphorus, Sulfur Silicon Relat. Elem. 2011, 186, 1032–1045; (d) Meadows , D. C. ; Gervay-Hague , J. Vinyl sulfones: Synthetic preparations and medicinal chemistry applications. Med. Res. Rev. 2006, 26, 793–814; (e) Liu , S. ; Zhou , B. ; Yang , H. ; He , Y. ; Jiang , Z-X. ; Kumar , S. ; Wu , L. ; Zhang , Z.-Y. Aryl vinyl sulfonates and sulfones as active site-directed and mechanism-based probes for protein tyrosine phosphatases. J. Am. Chem. Soc. 2008, 130, 8251–8260.
   Google Scholar
• For cysteine protease inhibitors, see (a) Liu , S. ; Hanzlik , R. P. Structure–activity relationships for inhibition of papain by peptide Michael acceptors . J. Med. Chem. 1992 , 35 , 1067 – 1075 ; (b) Palmer , J. T. ; Rasnick , D. ; Klaus , J. L. ; Brömme , D. Vinyl sulfones as mechanism-based cysteine protease inhibitors . J. Med. Chem. 1995 , 38 , 3193 – 3196 ; (c) Roush , W. R. ; Gwaltney II , S. L. ; Cheng , J. ; Scheidt , K. A. ; McKerrow , J. H. ; Hansell , E. Vinyl sulfonate esters and vinyl sulfonamides: Potent, irreversible inhibitors of cysteine proteases . J. Am. Chem. Soc. 1998 , 120 , 10994 – 10995 ; (d) Shenai , B. R. ; Lee , B. J. ; Alvarez-Hernandez , A. ; Chong , P. Y. ; Emal , C. D. ; Neitz , R. J. ; Roush , W. R. ; Rosenthal , P. J. Structure–activity relationships for inhibition of cysteine protease activity and development of Plasmodium falciparum by peptidyl vinyl sulfones . Antimicrob. Agents Ch. 2003 , 47 , 154 – 160 ; (e) Wang , G. ; Mahesh , U. ; Chen , G. Y. J. ; Yao , S. Q. Solid-phase synthesis of peptide vinyl sulfones as potential inhibitors and activity-based probes of cysteine proteases . Org. Lett. 2003 , 5 , 737 – 740 ; (f) Ettari , R. ; Nizi , E. ; Francesco , M. E. D. ; Dude , M.-A. ; Pradel , G. ; Vičík , R. ; Schirmeister , T. ; Micale , N. ; Grasso , S. ; Zappalà , M. Development of peptidomimetics with a vinyl sulfone warhead as irreversible falcipain-2 inhibitors . J. Med. Chem. 2008 , 51 , 988 – 996 . For HIV-1 inhibitors, see (g) Meadows , D. C. ; Sanchez , T. ; Neamati , N. ; North , T. W. ; Gervay-Hague , J. Ring substituent effects on biological activity of vinyl sulfones as inhibitors of HIV-1 . Bioorg. Med. Chem. 2007 , 15 , 1127 – 1137 . For sortase inhibitors, see (h) Frankel , B. A. ; Bentley , M. ; Kruger , R. G. ; McCafferty , D. G. Vinyl sulfones: Inhibitors of SrtA, a transpeptidase required for cell wall protein anchoring and virulence in Staphylococcus aureus . J. Am. Chem. Soc. 2004 , 126 , 3404 – 3405 . For tyrosine phosphatase inhibitors, see (i) Liu , S. ; Zhou , B. ; Yang , H. ; He , Y. ; Jiang , Z.-X. ; Kumar , S. ; Wu , L. ; Zhang , Z.-Y. Aryl vinyl sulfonates and sulfones as active site-directed and mechanism-based probes for protein tyrosine phosphatases . J. Am. Chem. Soc. 2008 , 130 , 8251 – 8260 .
   PubMed Web of Science ®Google Scholar
• Vinyl sulfones as Michael acceptors, see (a) Farthing , C. N. ; Marsden , S. P. Chiral vinyl dioxazaborocines in synthesis: Asymmetric cuprate additions to β-boronyl acrylates and vinyl sulfones . Tetrahedron Lett. 2000 , 41 , 4235 – 4238 ; (b) Esteves , A. P. ; Silva , M. E. ; Rodrigues , L. M. ; Oliveira-Campos , A. M. F. ; Hrdina , R. Aza-Michael reactions with vinyl sulfones and amberlyst-15 as catalyst . Tetrahedron Lett. 2007 , 48 , 9040 – 9043 ; (c) Sulzer-Mossé , S. ; Alexakis , A. ; Mareda , J. ; Bollot , G. ; Bernardinelli , G. ; Filinchuk , Y. Enantioselective organocatalytic conjugate addition of aldehydes to vinyl sulfones and vinyl phosphonates as challenging Michael acceptors . Chem. Eur. J. 2009 , 15 , 3204 – 3220 . Vinyl sulfones as dienophiles, see (d) Carr , R. V. C. ; Paquette , L. A. An ethylene and terminal olefin equivalent in [4 + 2]π cycloadditions: General synthetic application of phenyl vinyl sulfone to the construction of functionalized six-membered rings . J. Am. Chem. Soc. 1980 , 102 , 853 – 855 ; (e) Krasovsky , A. L. ; Nenajdenko , V. G. ; Balenkova , E. S. Diels–Alder reactions of β-trifluoroacetylvinylsulfones . Tetrahedron 2001 , 57 , 201 – 209 ; (f) Padwa , A. ; Lipka , H. ; Watterson , S. H. ; Murphree , S. S. Phenylsulfonyl ene-allenes as efficient precursors to bicyclic systems via intramolecular [2 + 2]-cycloaddition reactions . J. Org. Chem. 2003 , 68 , 6238 – 6250 ; (g) Llamas , T. ; Arrayás , R. G. ; Carretero , J. C. Catalytic enantioselective 1,3-dipolar cycloaddition of azomethine ylides with vinyl sulfones . Org. Lett. 2006 , 8 , 1795 – 1798 ; (h) López-Pérez , A. ; Robles-Machín , R. ; Adrio , J. ; Carretero , J. C. Oligopyrrole synthesis by 1,3-dipolar cycloaddition of azomethine ylides with bissulfonyl ethylenes . Angew. Chem. Int. Ed. 2007 , 46 , 9261 – 9264 ; (i) Gao , Y. ; Lam , Y. [3 + 2] Cycloaddition reactions in the synthesis of triazolo[4,5-b]pyridin-5-ones and pyrrolo[3,4-b]pyridin-2-ones . J. Comb. Chem. 2008 , 10 , 327 – 332 .
   Web of Science ®Google Scholar
• β-Elimination and sulfur oxidation: (a) Brace , N. O. An economical and convenient synthesis of phenyl vinyl sulfone from benzenethiol and 1,2-dichloroethane. J. Org. Chem. 1993, 58, 4506–4508; (b) Kroll , F. E. K. ; Morphy , R. ; Rees , D. ; Gani , D. Resin-immobilised benzyl and aryl vinyl sulfones: New versatile traceless linkers for solid-phase organic synthesis. Tetrahedron Lett. 1997, 38, 8573–8576; (c) Orita , A. ; Katakami , M. ; Yasui , Y. ; Kurihara , A. ; Otera , J. Integrated chemical process for green chemistry: One-pot synthesis of 3-substituted 5-(β-sulfonylvinyl)indoles by in situ generation of toxic vinyl sulfone. Green Chem. 2001, 3, 13–16; (d) Magnier , E. ; Tordeux , M. ; Goumont , R. ; Magder , K. ; Wakselman , C. Perfluoroalkylation of 2-mercaptoethanol as a key step for a new synthesis of perfluoroalkyl vinyl sulfides, sulfoxides, and sulfones. J. Fluorine Chem. 2003, 124, 55–59. Addition of ArSO2X followed by elimination: (e) da Silva Corrêa , C. M. M. ; Waters , W. A. Reactions of the free toluene-p-sulphonyl radical, part 1: Diagnostic reactions of free radicals. J. Chem. Soc. C 1968, 1874–1879; (f) Liu , L. K. ; Chi , Y. ; Jen , K.-Y. Copper-catalyzed additions of sulfonyl iodides to simple and cyclic alkenes. J. Org. Chem. 1980, 45, 406–410; (g) Harwood , L. M. ; Julia , M. ; Thuillier , G. L. Organic synthesis with sulphones, XVII: The anti-Markownikoff halosulphonylation of olefins via an ionic pathway, and a new method of preparing benzenesulphonyl iodide. Tetrahedron 1980, 36, 2483–2487; (h) Inomata , K. ; Kobayashi , T. ; Sasaoka , S. ; Kinoshita , H. ; Kotake , H. Convenient methods for the preparation of vinylic and allylic sulfones from alkenes. Chem. Lett. 1986, 289–292; (i) Nájera , C. ; Baldó , B. ; Yus , M. Regio- and stereo-selective synthesis of β-sulphonyl-α,β-unsaturated carbonyl compounds via an iodosulphonylation–dehydroiodination reaction. J. Chem. Soc., Perkin Trans. 1 1988, 1029–1032; (j) Nájera , C. ; Sansano , J. M. ; Yus , M. One-pot iodosulfonylation dehydroiodination of alkene: (E)-β-Tosylstyrene. J. Chem. Educ. 1995, 72, 664–665; (k) Nair , V. ; Augustine , A. ; George , T. G. ; Nair , L. G. An efficient one-pot synthesis of vinyl sulphones via CAN-mediated reaction of aryl sulphinates and alkenes. Tetrahedron Lett. 2001, 42, 6763–6765; (l) Nair , V. ; Augustine , A. ; Suja , T. D. CAN-mediated reaction of aryl sulfinates with alkenes and alkynes: Synthesis of vinyl sulfones, β-iodovinyl sulfones, and acetylenic sulfones. Synthesis 2002, 2259–2265; (m) Zhu , S. ; Qin , C. ; Xu , G. ; Chu , Q. A convenient synthesis of a new push–pull alkenes: β-Alkoxyl vinyl trifluoromethyl sulfones. Tetrahedron Lett. 1998, 39, 5265–5268; (n) Back , T. G. ; Collins , S. Selenosulfonation: Boron trifluoride catalyzed or thermal addition of selenosulfonates to olefins: A novel regio- and stereocontrolled synthesis of vinyl sulfones. J. Org. Chem. 1981, 46, 3249–3256; (o) Sas , W. The arenesulphonomercuriation of alkenes—A route to vinyl sulphones. J. Chem. Soc., Chem. Commun. 1984, 862–863; (p) Qian , H. ; Huang , X. Polystyrene-supported selenosulfonates: Efficient reagents for regio- and stereocontrolled synthesis of vinyl sulfones. Synlett 2001, 1913–1916; (q) Edwards , G. L. ; Muldoon , C. A. ; Sinclair , D. J. Cyclic enol ether synthesis via arenesulfonyl iodide additions to alkynols. Tetrahedron 1996, 52, 7779–7788; (r) Liu , X. ; Duan , X. ; Pan , Z. ; Han , Y. ; Liang , Y. Stereoselective synthesis of (Z)-β-chlorovinyl sulfones by addition of sulfonyl chlorides to acetylenes. Synlett 2005, 1752–1754. Horner–Wadsworth–Emmons reaction: (s) Popoff , I. C. ; Dever , J. L. ; Leader , G. R. α, β-Unsaturated sulfones via phosphonate carbanions. J. Org. Chem. 1969, 34, 1128–1130; (t) Wang , G. ; Yao , S. Q. Combinatorial synthesis of a small-molecule library based on the vinyl sulfone scaffold. Org. Lett. 2003, 5, 4437–4440. Hydrometallation reaction: (u) Huang , X. ; Duan , D.-H. The synthesis of ethenyl bifunctional reagents containing a sulfone moiety and zirconium by the abnormal addition of Cp2Zr(H)Cl to internal acetylenic sulfones. Chem. Commun. 1999, 1741–1742; (v) Huang , X. ; Duan , D. ; Zheng , W. Studies on hydrozirconation of 1-alkynyl sulfoxides or sulfones and the application for the synthesis of stereodefined vinyl sulfoxides or sulfones. J. Org. Chem. 2003, 68, 1958–1963; (w) Duan , D.-H. ; Huang , X. A facile regio- and stereocontrolled synthesis of (E)-disubstituted vinyl sulfones via transformation of alkenylzirconocenes with sulfonyl chlorides. Synlett 1999, 317–318; (x) Huang , X. ; Liang , C.-G. ; Xu , Q. ; He , Q.-W. Alkyne-based, highly stereo- and regioselective synthesis of stereodefined functionalized vinyl tellurides. J. Org. Chem. 2001, 66, 74–80. Selenosulfonation of alkynes: (y) Back , T. G. ; Collins , S. ; Krishna , M. V. ; Law , K.-W. Substitution reactions of organocuprates with β-(phenylseleno)vinyl sulfones derived from the selenosulfonation of acetylenes: A convenient and stereospecific preparation of vinyl sulfones and olefins from acetylenes. J. Org. Chem. 1987, 52, 4258–4264; (z) Back , T. G. ; Bethell , R. J. ; Parvez , M. ; Wehrli , D. Additions of organocopper reagents and heteroatom nucleophiles to 1-phenylseleno-2-(p-toluenesulfonyl)ethyne: Preparation of vinyl and allenic sulfones and formation of Michael, anti-Michael, and rearrangement products. J. Org. Chem. 1998, 63, 7908–7919; (aa) Watanabe , S. ; Yamamoto , K. ; Itagaki , Y. ; Iwamura , T. ; Iwama , T. ; Kataoka , T. ; Tanabe , G. ; Muraoka , O. Synthesis and reactivity of β-sulfonylvinylselenonium salts: A simple stereoselective synthesis of β-functionalized (Z)-vinyl sulfones. J. Chem. Soc., Perkin Trans. 1 2001, 239–247. Palladium-catalyzed reactions: (ab) Berteina , S. ; Wendeborn , S. ; Brill , W. K.-D. ; Mesmaeker , A. D. Pd-mediated C-C bond formation with olefins and acetylenes on solid support: A scope and limitations study. Synlett 1998, 676–678; (ac) Cacchi , S. ; Fabrizi , G. ; Goggiamani , A. ; Parisi , L. M. ; Bernini , R. Unsymmetrical diaryl sulfones and aryl vinyl sulfones through palladium-catalyzed coupling of aryl and vinyl halides or triflates with sulfinic acid salts. J. Org. Chem. 2004, 69, 5608–5614; (ad) Kabalka , G. W. ; Guchhait , S. K. Convenient synthesis of α, β-unsaturated sulfones via a Mizoroki–Heck reaction of arylboronic acids with phenyl vinyl sulfones. Tetrahedron Lett. 2004, 45, 4021–4022; (ae) Reeves , D. C. ; Rodriguez , S. ; Lee , H. ; Haddad , N. ; Krishnamurthy , D. ; Senanayake , C. H. Palladium-catalyzed coupling of vinyl tosylates with arylsulfinate salts. Tetrahedron Lett. 2009, 50, 2870–2873. Copper-catalyzed reactions: (af) Bao , W. ; Wang , C. CuI/L-proline potassium salt–catalysed synthesis of vinyl sulfones via coupling reaction of vinyl bromides with sulfinic acid salts in ionic liquid. J. Chem. Res. 2006, 6, 396–397; (ag) Bian , M. ; Xu , F. ; Ma , C. Anion-functionalized ionic liquids enhance the CuI-catalyzed cross-coupling reaction of sulfinic acid salts with aryl halides and vinyl bromides. Synthesis 2007, 2951–2956. Cross-metathesis reactions: (ah) Grela , K. ; Bieniek , M. Highly selective cross-metathesis with phenyl vinyl sulphone using the “second-generation” Grubbs’ catalyst. Tetrahedron Lett. 2001, 42, 6425–6428; (ai) Michrowska , A. ; Bieniek , M. ; Kim , M. ; Klajn , R. ; Grela , K. Cross-metathesis reaction of vinyl sulfones and sulfoxides. Tetrahedron 2003, 59, 4525–4531. Reaction of 1,2-dibromoalkanes with sulfinic acid sodium salts: (aj) Guan , Z.-H. ; Zuo , W. ; Zhao , L.-B. ; Ren , Z.-H. ; Liang , Y.-M. An economical and convenient synthesis of vinyl sulfones. Synthesis 2007, 1465–1470.
   Web of Science ®Google Scholar
• (a) Xu , Q.-L. ; Dai , L.-X. ; You , S.-L. Tandem Ir-catalyzed allylic substitution reaction of allyl sulfinates and isomerization . Org. Lett. 2010 , 12 , 800 – 803 ; (b) Taniguchi , N. Stereoselective synthesis of (E)-alkenyl sulfones from alkenes or alkynes via copper-catalyzed oxidation of sodium sulfinates . Synlett 2011 , 1308 – 1312 ; (c) Das , B. ; Lingaiah , M. ; Damodar , K. ; Bhunia , N. An efficient synthesis of vinyl sulfones from alkenes and aryl sulfinates . Synthesis 2011 , 2941 – 2944 ; (d) Song , R.-J. ; Liu , Y. ; Liu , Y.-Y. ; Li , J.-H. Palladium-catalyzed conjugate addition to electron-deficient alkynes with benzenesulfinic acid derived from 1,2-bis(phenylsulfonyl)ethane: Selective synthesis of (E)-vinyl sulfones . J. Org. Chem. 2011 , 76 , 1001 – 1004 .
   PubMed Web of Science ®Google Scholar
• Katrun , P. ; Chiampanichayakul , S. ; Korworapan , K. ; Pohmakotr , M. ; Reutrakul , V. ; Jaipetch , T. ; Kuhakarn , C. PhI(OAc)2/KI-mediated reaction of aryl sulfinates with alkenes, alkynes, and α, β-unsaturated carbonyl compounds: Synthesis of vinyl sulfones and β-iodovinyl sulfones . Eur. J. Org. Chem. 2010 , 5633 – 5641 .
   Web of Science ®Google Scholar
• For reviews, see (a) Togo , H. ; Iida , S. Synthetic use of molecular iodine for organic synthesis. Synlett 2006, 2159–2175; (b) Banerjee , A. K. ; Vera , W. ; Mora , H. ; Laya , M. S. ; Bedoya , L. ; Cabrera , E. V. Iodine in organic synthesis. J. Sci. Ind. Res. 2006, 65, 299–308; (c) Das , S. ; Borah , R. ; Devi , R. R. ; Thakur , A. J. Molecular iodine in protection and deprotection chemistry. Synlett 2008, 2741–2762; (d) Jereb , M. ; Vražič , D. ; Zupan , M. Iodine-catalyzed transformation of molecules containing oxygen functional groups. Tetrahedron 2011, 67, 1355–1387; (e) Banerjee , A. K. ; Laya , M. S. ; Cabrera , E. V. Iodocyclization: Past and present examples. Curr. Org. Chem. 2011, 15, 1058–1080.
   Web of Science ®Google Scholar
• (a) Padwa , A. ; Ishida , M. Silver tetrafluoroborate induced reaction of trimethylsilyl enol ethers with 2,3-diiodo-1-(phenylsulfonyl)-1-propene as a method for preparing substituted furans . Tetrahedron Lett. 1991 , 32 , 5673 – 5676 ; (b) Rao , C. J. ; Knochel , P. A direct preparation of vinylogous acyl anion equivalents . J. Org. Chem. 1991 , 56 , 4593 – 4596 (c) Knochel , P. ; Rao , C. J. Preparation and reactivity of functionalized alkenyl-zinc, -copper, and -chromium organometallics . Tetrahedron 1993 , 49 , 29 – 48 ; (d) Short , K. M. ; Ziegler , C. B. Jr. 5- and 6-membered ring compounds from (E)-β-iodo(vinyl)sulfones . Tetrahedron Lett. 1995 , 36 , 355 – 356 ; (e) Zoller , T. ; Uguen , D. An efficient procedure for preparing γ-hydroxy α, β-unsaturated sulfones . Eur. J. Org. Chem. 1999 , 1545 – 1550 ; (f) Gu , X.-X. ; Xie , M.-H. ; Zhao , X.-Y. ; Sun , Y. ; Zhang , W. ; Xie , F.-D. ; Wang , S.-W. An efficient synthesis of polysubstituted 1,3-enynes from (E)-β-iodovinyl sulfones and terminal alkynes . Chin. J. Chem. 2008 , 26 , 1625 – 1629 .
   Web of Science ®Google Scholar
• (a) Fu , C. ; Xu , C. ; Huang , Z.-Z. ; Huang , X. α, β-Unsaturated sulfones by the Wittig reaction of stable ylide with aldehydes under microwave irradiation . Org. Prep. Proced. Internat. 1997 , 29 , 587 – 589 ; (b) Kamigata , N. ; Sawada , H. ; Kobayashi , M. Reactions of arenesulfonyl chlorides with olefins catalyzed by a ruthenium(I1) complex . J. Org. Chem. 1983 , 48 , 3793 – 3796 .
   Web of Science ®Google Scholar
• Deng , G. ; Zou , J. The first nucleophilic substitution reaction of organoindium reagents with sulfonyl chlorides: A facile method for preparation of vinyl sulfones . Arkivoc 2010 , 2 , 186 – 194 .
   Web of Science ®Google Scholar
• Nair , V. ; Augustine , A. ; Panicker , S. ; Suja , T. D. ; Mathai , S. Cerium(IV) ammonium nitrate (CAN)–mediated sulfonylation of styrenes: Some interesting observations . Res. Chem. Intermed. 2003 , 29 , 213 – 226 .
   Web of Science ®Google Scholar
• Holler , M. ; Sin , H. S. ; James , A. ; Burger , A. ; Trintsch , D. ; Biellmeann , J.-F. (E)-1-Alkyl-4-[2-(alkylsulfonyl)-1-ethenyl]pyridinium salts: Reaction of thiol groups giving rise to chromophoric (E)-1-alkyl-4-[2-(alkylsulfanyl)-1-ethenyl]pyridinium salts . Chem. Eur. J. 2000 , 6 , 2053 – 2062 .
   PubMed Web of Science ®Google Scholar
• Jang , W. B. ; Jeon , H. J. ; Oh , D. Y. Direct sulfonylation of lithiated alkyl phosphonates with benzenesulfonyl fluoride: Facile method for preparation of α -sulfonyl alkyl phosphonates and vinyl sulfones . Synth. Commun. 1998 , 28 , 1253 – 1256 .
   Web of Science ®Google Scholar
• Kazuyoshi , T. ; Kanoko , T. ; Maki , M. ; Haruo , O. Single-step preparation of allylic sulfides having 1-phenyltetrazole-5-thio group from allylic alcohols using S,S′-bis(1-phenyl-1H-tetrazol-5-yl) dithiocarbonate and reactions involving the allylic sulfides . Tetrahedron Lett. 1988 , 29 , 4105 – 4108 .
   Web of Science ®Google Scholar
• Inomata , K. ; Hirata , T. ; Sasada , Y. ; Asada , T. ; Senda , H. ; Kinoshita , H. Crystallographic approach to the origin of “syn effect.” Chem. Lett. 1990 , 12 , 2153 – 2156 .
   Web of Science ®Google Scholar
• (a) Mori , Y. ; Yaegashi , K. ; Furukawa , H. Synthesis of trans-fused tetrahydropyrans via intramolecular cyclization of α -bromo-γ’-hydroxy ketones . Tetrahedron Lett. 1999 , 40 , 7239 – 7242 ; (b) Ashwell , M. ; Clegg , W. ; Jackson , R. F. W. Phenylsulphonyloxiranes as functionalised acyl anion equivalents in organic synthesis . J. Chem. Soc., Perkin Trans. 1 1991 , 897 – 908 .
   Web of Science ®Google Scholar