Allylic selenosulfide rearrangement: A new method for chemical ligation to cysteine and other thiols

ORGN 187

David Crich, Venkataramanan Krishnamurthy, Thomas K. Hutton, thutton@uic.edu, Yekui Zou, Franck Brebion, and Fan Yang. Department of Chemistry, University of Illinois at Chicago, 845 W. Taylor St, Room 4500, Chicago, IL 60607-7061
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.
 

New Reactions and Methodology
8:00 AM-12:00 PM, Monday, 27 March 2006 Georgia World Congress Center -- C301, Oral

Division of Organic Chemistry

The 231st ACS National Meeting, Atlanta, GA, March 26-30, 2006