Allylic selenosulfide rearrangement: a method for chemical ligation to cysteine and other thiols.
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.
Crich
David
D
Department of Chemistry, University of Illinois at Chicago, 60607-7061, USA. dcrich@uic.edu
Krishnamurthy
Venkataramanan
V
Hutton
Thomas K
TK
D000498:Allyl Compounds / Q000737:chemistry*; D003545:Cysteine / Q000031:analogs & derivatives* / Q000737:chemistry; D009842:Oligopeptides / Q000737:chemistry*; D012643:Selenium / Q000737:chemistry; D018036:Selenium Compounds / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013440:Sulfides / Q000138:chemical synthesis*
D000498:Allyl Compounds; D009842:Oligopeptides; D018036:Selenium Compounds; D013438:Sulfhydryl Compounds; D013440:Sulfides; D012643:Selenium; D003545:Cysteine