Stereomodulating effect of remote groups on the NADH-mimetic reduction of alkyl aroylformates with 1,4-dihydronicotinamide-β-lactam amides

被引：7

作者：

Aizpurua, Jesus M. ^{[1
]}

Palomo, Claudio ^{[1
]}

Fratila, Raluca M. ^{[1
]}

Ferron, Pablo ^{[1
]}

Miranda, Jose I. ^{[1
]}

机构：

[1] Univ Basque Country, Dept Quim Organ 1, Joxe Mari Korta R&D Ctr, San Sebastian 20018, Spain

来源：

TETRAHEDRON | 2010年 / 66卷 / 17期

关键词：

NADH; beta-Lactams; DFT calculations; Enantioselective reduction; HOMOCHIRAL AUXILIARY (ETA-5-C5H5)FE(CO)(PPH3); BETA-HYDROXY-CARBOXAMIDE; ASYMMETRIC REDUCTION; MODEL COMPOUNDS; CHIRAL 1,4-DIHYDROPYRIDINES; STEREOSELECTIVE REDUCTION; ETHYL BENZOYLFORMATE; HIGH ENANTIOSELECTIVITY; METHYL BENZOYLFORMATE; HYDRIDE TRANSFER;

D O I：

10.1016/j.tet.2010.02.085

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Conformationally restricted NADH peptidomimetics 4a-e, characterized by the presence of a (1,4-dihydronicotinamide)-(beta-lactam) moiety, have been synthesized and used to study the Mg2+ cation-promoted asymmetric reduction of alkyl aroylformates in acetonitrile. Increasing the bulkiness of peripheral substituents at the nitrogen atom of the beta-lactam ring, at the 1,4-dihydronicotinamide moiety, or at the aroylformate ester group, was found to cause weak but clearly detectable variations of the enantiomeric excess of the reaction. A rational for these observations was consistent with a chelated NADH/Mg2+/ArCOCO2R3 ternary complex model, according to DFT calculations computed at a B3LYP/631G(sic) theory level. (C) 2010 Elsevier Ltd. All tights reserved.

引用

页码：3187 / 3194

页数：8

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