Cooperative Thiourea-Bronsted Acid Organocatalysis: Enantioselective Cyanosilylation of Aldehydes with TMSCN

被引：94

作者：

Zhang, Zhiguo ^{[1
]}

Lippert, Katharina M. ^{[1
]}

Hausmann, Heike ^{[1
]}

Kotke, Mike ^{[1
]}

Schreiner, Peter R. ^{[1
]}

机构：

[1] Univ Giessen, Inst Organ Chem, D-35392 Giessen, Germany

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2011年 / 76卷 / 23期

关键词：

DYNAMIC KINETIC RESOLUTION; PRIMARY AMINE-THIOUREA; DIRECT CONJUGATE ADDITION; PICTET-SPENGLER REACTIONS; NITRO-MICHAEL ADDITION; BIFUNCTIONAL ORGANOCATALYSTS; ASYMMETRIC CATALYSIS; CARBOXYLATE COMPLEXATION; TRANSFER HYDROGENATION; CYANOHYDRIN SYNTHESIS;

D O I：

10.1021/jo201864e

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

We report a new thiourea-Bronsted acid cooperative catalytic system for the enantioselective cyanosilylation of aldehydes with yields up to 90% and enamioselectivities up to 88%. The addition of an achiral acid was found to be crucial for high asymmetric induction. Mechanistic investigations using a combination of NMR, ESI-MS, and density functional theory computations (including solvent corrections) at the M06/6-31G(d,p) level of theory suggest that the key catalytic species results from the cooperative interaction of bifunctional thioureas and an achiral acid that form well-defined chiral hydrogen-bonding environments.

引用

页码：9764 / 9776

页数：13

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