A Practical Synthesis of Mixed Allyl and Allenesulfinates

Abstract

A new, general, and efficient method for the preparation of mixed sulfoxylates (ROSOR′) by treatment of symmetrical dialkoxy disulfides (ROSSOR) with alcohols at room temperature has been found. Subsequent spontaneous [2,3]-sigmatropic rearrangements of mixed sulfoxylates such as alkyl allyl and alkyl propargyl sulfoxylates afford mixed alkyl allyl and alkyl allenesulfinates in good yield. The latter are not readily available by other routes.

Key words

alkynes - alkenes - dialkoxy disulfides - sulfinates - [2,3]-sigmatropic rearrangements

References

• 1a Braverman S. Ph.D. Thesis   University of Alberta; Edmonton, Canada: 1963. 
• 1b Braverman S. Stabinsky Y. J. Chem. Soc., Chem. Commun.  1967,  270 
• 1c Braverman S. Stabinsky Y. Isr. J. Chem.  1967,  5:  125 
• 1d Braverman S. Mechoulam H. Isr. J. Chem.  1967,  5:  71 
• 1e Braverman S. Mechoulam H. Tetrahedron  1974,  30:  3883 
• 2a Braverman S. In Chemistry of Sulfones and Sulfoxides   Patai S. Rappoport Z. Stirling CJM. Wiley; New York: 1988.  Chap. 13.
• 2b Braverman S. In Chemistry of Sulfones and Sulfoxides   Patai S. Rappoport Z. Stirling CJM. Wiley; New York: 1988.  Chap. 14.
• 2c Braverman S. In The Chemistry of Sulfinic Acids, Esters and their Derivatives   Patai S. Wiley; New York: 1990.  Chap. 11.
• 2d Braverman S. In The Chemistry of Sulfenic Acids and their Derivatives   Patai S. Wiley; New York: 1990.  Chap. 8.
• 3 Hassner A. Stumer C. Organic Synthesis Based on Named Reactions and Unnamed Reactions   Pergamon; Oxford: 1994.  p.266 
• 4 Braverman S. Segev D. J. Am. Chem. Soc.  1974,  96:  1245 
• 5a Nicolaou KC. Skokotas G. Maligres P. Zuccarello G. Schweiger EJ. Toshima K. Wenderborn S. Angew. Chem., Int. Ed. Engl.  1989,  28:  1272 
• 5b Nicolaou KC. Smith AL. In Modern Acetylene Chemistry   Stang PJ. Diedrich F. VCH; Weinheim: 1995.  Chap. 7.
• 6a Braverman S. Zafrani Y. Gottlieb HE. Tetrahedron Lett.  2000,  41:  2679 
• 6b Braverman S. Zafrani Y. Gottlieb HE. Tetrahedron  2001,  57:  9177 
• 6c Braverman S. Cherkinsky M. Birsa ML. Zafrani Y. Eur. J. Org. Chem.  2002,  3198 
• 7 Thompson QE. Crutchfield MM. Dietrich MW. J. Org. Chem.  1965,  30:  2692 
• 8 Braverman S. Pechenick T. Tetrahedron Lett.  2002,  43:  499 
• 9 Braverman S. Pechenick T. Gottlieb EH. Tetrahedron Lett.  2003,  44:  777 
• 10a Freeman F. Chem. Rev.  1984,  84:  117 
• 10b Lacombe SM. Rev. Heteroatom Chem.  1999,  21:  1 
• 11a Block E. Angew. Chem., Int. Ed. Engl.  1992,  31:  1135 
• 11b Block E. Thiruvazhi M. Toscano PJ. Bayer T. Grisoni S. Zhao SH. J. Am. Chem. Soc.  1996,  118:  2790 
• 11c Block E. Bayer T. Naganathan S. Zhao SH. J. Am. Chem. Soc.  1996,  118:  2799 
• 12a Braverman S. Reisman D. Tetrahedron Lett.  1977,  1753 
• 12b Reisman D. Ph. D. Thesis   Bar-Ilan University; Ramat-Gan: 1985.