Addition of Bis-sulfinyl Anions to Ketones: Stereoselective Synthesis of Allylic Alcohols through Evans-Mislow Rearrangement Based Domino Reactions

Abstract

Enantiopure cyclic allylic alcohols were obtained from cyclic ketones and bis-sulfoxides through a domino reaction mixing anionic and concerted elementary steps. Total transfer of chirality was achieved, presumably through cooperative effects of both sulfoxides units. Depending on the ring size, both sulfinyl groups could be converted, giving C ₂-symmetric bis-allylic alcohols.

Key words

alkenation - carbanion - pericyclic reaction - sulfoxide - sulfur

References

• 1a Bickart P. Carson FW. Jacobus J. Miller EG. Mislow K. J. Am. Chem. Soc.  1968,  90:  4869 
• 1b Evans DA. Andrews GC. Acc. Chem. Res.  1974,  7:  147 
• 1c Hoffmann RW. Angew. Chem., Int. Ed. Engl.  1979,  18:  563 
• For rearrangements involving sulfoxides, see:
• 1d Braverman S. In The Chemistry of Sulphones and Sulphoxides   Patai S. Rappoport Z. Stirling CJM. John Wiley; London: 1988.  p.717 
• For [2,3] sigmatropic rearrangements, see:
• 1e Ritter K. In Houben-Weyl   4th ed., Vol. E 21:  Helmchen G. Hoffmann RW. Mulzer J. Schaumann E. Thieme; Stuttgart: 1996.  p.4971 
• 2a Tanikaga R. Nozaki Y. Tamura T. Kaji A. Synthesis  1983,  134 
• 2b Ono T. Tamaoka T. Yuasa Y. Matsuda T. Nokami J. Wakabayashi S. J. Am. Chem. Soc.  1984,  106:  7890 
• 2c Nokami J. Kataoka K. Shiraishi K. Osafune M. Hussain I. Sumida S.-I. J. Org. Chem.  2001,  66:  1228 
• 2d Trost BM. Grese TA. J. Org. Chem.  1991,  56:  3189 
• 3a Burgess K. Henderson I. Tetrahedron Lett.  1989,  30:  3633 
• For a different and more selective cascade, see:
• 3b Arce E. Carreño MC. Cid MB. Garcìa Ruano JL. J. Org. Chem.  1994,  59:  3421 
• 3c Carreño MC. Cid MB. Garcìa Ruano JL. Tetrahedron: Asymmetry  1996,  7:  2151 
• 4 Guerrero-de la Rosa V. Ordoñez M. Alcudia F. Llera JM. Tetrahedron Lett.  1995,  36:  4889 
• 5a Delouvrié B. Nájera F. Fensterbank L. Malacria M. J. Organomet. Chem.  2002,  643-644:  130 
• 5b Brebion F. Vitale M. Fensterbank L. Malacria M. Tetrahedron: Asymmetry  2003,  14:  2889 
• 5c Brebion F. Delouvrié B. Nájera F. Fensterbank L. Malacria M. Vaissermann J. Angew. Chem. Int. Ed.  2003,  42:  5342 
• 5d Brebion F. Goddard J.-P. Fensterbank L. Malacria M. Synthesis  2005,  2449 
• 5e Brebion F. Goddard J.-P. Gomez C. Fensterbank L. Malacria M. Synlett  2006,  713 
• 6 Additions of the anion derived from Aggarwal’s cyclic bis-sulfoxide to not to sterically demanding ketones led to the corresponding bis-sulfinyl alcohols, without further reaction: Aggarwal VK. Franklin R. Maddock J. Evans GR. Thomas A. Mahon MF. Molloy KC. Rice MJ. J. Org. Chem.  1995,  60:  2174 
• 7 Sugimura T. Iguchi H. Tsuchida R. Tai A. Nishiyama N. Hakushi T. Tetrahedron: Asymmetry  1998,  9:  1007 
• 8 The properties of alkene carbenium ions and carbanions: Richey HGJ. In The Chemistry of Alkenes   Vol. 2:  Zabicky J. John Wiley; London: 1970.  p.39 
• 9a Annunziata R. Cinquini M. Cozzi F. Farina S. Montanari V. Tetrahedron  1987,  43:  1013 
• 9b Koprowski M. Krawczyk E. Skowroñska A. McPartlin M. Choi N. Radojevic S. Tetrahedron  2001,  57:  1105 
• 9c Zohar E. Stanger A. Marek I. Synlett  2005,  2239 
• 10 Hoffmann RW. Goldmann S. Gerlach R. Maak N. Chem. Ber.  1980,  113:  845 
• 11 Harada T. Wada I. Oku A. J. Org. Chem.  1989,  54:  2599