Unexpected subtilisin-catalyzed hydrolysis of a sulfinamide bond in preference to a carboxamide bond in N-acyl sulfinamides

Paul F. Mugford, Vladimir P. Magloire, Romas J. Kazlauskas

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

Subtilisin Carlsberg-catalyzed hydrolysis of N-chloroacetyl p-toluenesulfinamide favored cleavage of the sulfinamide (S(O)-N) bond with a minor amount (∼25%) of the expected carboxamide (C(O)-N) bond. The sulfinamide hydrolysis was enantioselective (E ∼ 17) and yielded remaining starting material enriched in the R-enantiomer and achiral product, sulfinic acid and chloroacetamide, as confirmed by mass spectra and NMR. In contrast, the related subtilisin BPN′ and E favored the carboxamide hydrolysis. Hydrolysis of the pseudo-symmetrical N-p-toluoyl p-toluenesulfinamide, which contains a sulfinamide and a carboxamide in similar steric and electronic environments, gave only sulfinamide cleavage (>10:1) for subtilisin Carlsberg, showing that sulfinamide cleavage is the preferred path even when a similar carboxamide is available.

Original languageEnglish (US)
Pages (from-to)6536-6537
Number of pages2
JournalJournal of the American Chemical Society
Volume127
Issue number18
DOIs
StatePublished - May 11 2005

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