Acid-Induced Rearrangement Reactions of α-Hydroxy-1,3-dithianes

Abstract

Secondary benzylic or aliphatic α-hydroxydithianes 1a-c rearrange to α-thioketones when treated with acid. Related tertiary alcohols 1d-g eliminate to dithioketene ketals (e.g., 2d), which are ring-opened to thiols in some cases (1e, 1f). Allylic α-hydroxydithianes 1h and 1i form the thioesters 2h and 2i (homologation), and the tertiary alcohols 1j and 1k undergo deoxygenation to 2j and 2k.

Key words

1,3-dithianes - dithioacetals - 1,3-dithian-1-oxides - rearrangement - deoxygenation - homologation

References

• 1a Wuts PGM. Greene TW. Greene’s Protective Groups in Organic Synthesis   4th ed.:  Wiley; New York: 2006. 
• 1b Kocienski PJ. Protecting Groups   3rd ed.:  Georg Thieme Verlag; Stuttgart: 2004. 
• 2a Smith AB. Adams C. Acc. Chem. Res.  2004,  37:  365 
• 2b Schaumann E. Kirschning A. Synlett  2007,  177 
• 2c Page PCB. van Niel MB. Prodger JC. Tetrahedron  1989,  45:  7643 
• 2d Gröbel B.-T. Seebach D. Synthesis  1977,  357 
• 2e Seebach D. Synthesis  1969,  17 
• 3 Krohn K. Cludius-Brandt S. Synthesis  2008,  1369 
• 4a Kuhn R. Baschang-Bister W. Dafeldecker W. Liebigs Ann. Chem.  1961,  641:  160 
• 4b Kuhn R. Neugebauer A. Chem. Ber.  1961,  94:  2629 
• 5a Behr S. Hegemann K. Schimanski H. Fröhlich R. Haufe G. Eur. J. Org. Chem.  2004,  3884 
• 5b Ong CW. Yu CY. Tetrahedron  2003,  59:  9677 
• 5c Wan Y. Barnhurst LA. Kutateladze AG. Org. Lett.  1999,  1:  937 
• 5d Afonso CAM. Barros MT. Godinho LS. Maycock CD. Synthesis  1991,  575 
• 5e Nickon A. Rodriguez AD. Shirhatti V. Ganguly R. J Org. Chem.  1985,  50:  4218 
• 5f Marshall JA. Roebke H. J. Org. Chem.  1969,  34:  4188 
• 5g Angibeaud P. Bosso C. Defaye J. Horton D. J. Chem. Soc., Perkin Trans. 1  1979,  1583 
• 5h Stork G. Cheung HT. J. Am. Chem. Soc.  1965,  87:  3783 
• 6 Seebach D. Corey EJ. J. Org. Chem.  1975,  40:  231 
• 7a

  We thank the referee for drawing our attention to this mechanism.

• 7b For an analogous reaction of vinyl sulfides to give α-thiolated ketones, see: Braun M. Tetrahedron Lett.  1978,  19:  3695 
• 8 Arad-Yellin R. Eaton DF. J. Am. Chem. Soc.  1982,  104:  6147 
• 9 Iranpoor N. Firouzabadi H. Shaterian HR. J. Org. Chem.  2002,  67:  2826 
• 10a Okuyama T. Fueno T. J. Am. Chem. Soc.  1980,  102:  6590 
• 10b Okuyama T. Kawao S. Fujiwara W. Fueno T. J. Org. Chem.  1984,  49:  89 
• 11 Carrey F. Neergaard JE. J. Org. Chem.  1971,  36:  2731