Synthesis of Allylic Sulfones and Their Conversion to Dienoic and Trienoic Acids

References

• 1974–1976 . Fellow of the Alfred P. Sloan Foundation
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• The conversion of t-butyl alkyl sulfoxides to ethyl esters of alkyl sulfinic acids with NCS in CHCl3-EtOH(1%) at 25° has been described by F. Jung and T. Durst, Chem. Comm., 4 (1973). This cleavage of the carbon-sulfur bond in the presence of allylic alcohols coupled with the sulfinate-sulfone rearrangement5 has considerable potential for the synthesis of dienes as well as trienes via the well known Ramberg-Bäcklund reaction2
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• Compound 5 was prepared from t-butyl mercaptide and methyl bromoacetate in methanol(80%) followed by oxidation with periodate(97%)
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• Thompson , Q. E. 1965 . J. Org. Chem. , 30 : 2703 For rearrangements of allylic sulfinates see S. Braverman, Int. J. Sulfur Chem., C, 6, 149 (1971); S. Braverman and D. Segev, J. Amer. Chem. Soc., 96, 1245 (1974); G. Büchi and R. M. Freidinger, J. Amer. Chem. Soc., 96, 3332 (1974)
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• Prior to use the chloroform was kept over P2O5 in order to remove traces of water and alcohol which are present. Failure to take this necessary precaution results in formation of ethyl sulfinate derivatives
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• Büchi and Freidinger5 have also observed that silica gel apparently catalyzes the sulfinate to sulfone rearrangement
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