Document Detail

Evidence for a Morin type intramolecular cyclization of an alkene with a phenylsulfenic acid group in neutral aqueous solution.
MedLine Citation:
PMID:  18500784     Owner:  NLM     Status:  MEDLINE    
Sulfenic acids (RSOH) are among the most common sulfur-centered reactive intermediates generated in biological systems. Given the biological occurrence of sulfenic acids, it is important to explore the reactivity of these intermediates under physiological conditions. The Morin rearrangement is a synthetic process developed for the conversion of penicillin derivatives into cephalosporins that proceeds via nucleophilic attack of an alkene on a sulfenic acid intermediate. In its classic form, the Morin reaction involves initial elimination of a sulfenic acid from a cyclic sulfoxide, followed by intramolecular cyclization of the resulting alkene and sulfenic acid groups to generate an episulfonium ion intermediate that undergoes further reaction to yield ring-expanded products. On the basis of the existing literature, it is difficult to assess whether the reaction between an alkene and a sulfenic group can occur under mild conditions because the conditions required to generate the sulfenic acid from the sulfoxide precursor in the Morin reaction typically involve high temperatures and strong acid. In the work described here, beta-sulfinylketone precursors were used to generate a "Morin type" sulfenic acid intermediate under mild conditions. This approach made it possible to demonstrate that the intramolecular cyclization of an alkene with a phenylsulfenic acid to generate an episulfonium ion intermediate can occur in neutral aqueous solution at room temperature.
Kripa Keerthi; Santhosh Sivaramakrishnan; Kent S Gates
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural     Date:  2008-05-23
Journal Detail:
Title:  Chemical research in toxicology     Volume:  21     ISSN:  1520-5010     ISO Abbreviation:  Chem. Res. Toxicol.     Publication Date:  2008 Jul 
Date Detail:
Created Date:  2008-07-22     Completed Date:  2008-09-11     Revised Date:  2014-09-12    
Medline Journal Info:
Nlm Unique ID:  8807448     Medline TA:  Chem Res Toxicol     Country:  United States    
Other Details:
Languages:  eng     Pagination:  1368-74     Citation Subset:  IM    
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MeSH Terms
Alkylating Agents / chemistry
Cycloparaffins / chemistry*
Sulfenic Acids / chemistry*
Water / chemistry
Grant Support
CA 119131/CA/NCI NIH HHS; CA 83925/CA/NCI NIH HHS; R01 CA083925/CA/NCI NIH HHS; R01 CA083925-08/CA/NCI NIH HHS; R01 CA119131/CA/NCI NIH HHS; R01 CA119131-03/CA/NCI NIH HHS
Reg. No./Substance:
0/Alkylating Agents; 0/Cycloparaffins; 0/Sulfenic Acids; 059QF0KO0R/Water

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine

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