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

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.

SUBMITTER: Crich D

PROVIDER: S-EPMC4658652 | biostudies-literature | 2006 Mar

REPOSITORIES: biostudies-literature

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

Crich David D Krishnamurthy Venkataramanan V Hutton Thomas K TK

Journal of the American Chemical Society 20060301 8

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 allyl ...[more]

PMID: 16492032

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