TY - JOUR
T1 - Unexpected subtilisin-catalyzed hydrolysis of a sulfinamide bond in preference to a carboxamide bond in N-acyl sulfinamides
AU - Mugford, Paul F.
AU - Magloire, Vladimir P.
AU - Kazlauskas, Romas J.
PY - 2005/5/11
Y1 - 2005/5/11
N2 - 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.
AB - 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.
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U2 - 10.1021/ja0506105
DO - 10.1021/ja0506105
M3 - Article
C2 - 15869266
AN - SCOPUS:18644365735
SN - 0002-7863
VL - 127
SP - 6536
EP - 6537
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 18
ER -