Journal of the American Chemical Society 2006-03-01

Allylic selenosulfide rearrangement: a method for chemical ligation to cysteine and other thiols.

David Crich, Venkataramanan Krishnamurthy, Thomas K Hutton

Index: J. Am. Chem. Soc. 128 , 2544, (2006)

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Abstract

Alkylation of potassium selenosulfate with allylic halides gives Se-allyl seleno Bunte salts. On reaction with thiols at room temperature, these afford mixed dialkyl selenosulfides, which undergo 2,3-sigmatropic rearrangement with loss of selenium, either spontaneously or with assistance by triphenylphosphine, thereby providing mixed dialkyl sulfides and a new permanent chemical ligation method. The process is illustrated through the lipidation of cysteine-containing tripeptides and by the allylation of 1-thioglucose tetraacetate.