Enantioselective Hydrosilylation of Ketones Catalyzed by a Readily Accessible N-Heterocyclic Carbene-Ir Complex at Room Temperature

被引：21

作者：

Shinohara, Kanako ^{[1
]}

Kawabata, Shun ^{[1
]}

Nakamura, Hanako ^{[1
]}

Manabe, Yoshiki ^{[1
]}

Sakaguchi, Satoshi ^{[1
]}

机构：

[1] Kansai Univ, Dept Chem & Mat Engn, Fac Chem Mat & Bioengn, Suita, Osaka 5648680, Japan

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2014年 / 2014卷 / 25期

基金：

日本学术振兴会;

关键词：

Asymmetric catalysis; Ligand design; Carbenes; Nitrogen heterocycles; Hydrosilylation; Iridium; ASYMMETRIC TRANSFER HYDROGENATION; TRANSITION-METAL-COMPLEXES; RHODIUM COMPLEXES; (TRIAZOLINYLIDENE)RHODIUM COMPLEXES; STEREODIRECTING LIGANDS; IRIDIUM COMPLEXES; HIGHLY EFFICIENT; COPPER; REDUCTION; BINAM;

D O I：

10.1002/ejoc.201402279

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A series of functionalized azolium compounds were synthesized from chiral alpha-amino acid derivatives such as beta-amino alcohols. Reaction of hydroxy-amide-functionalized azolium salts thus obtained with Ag2O afforded N-heterocyclic carbene-Ag (NHC-Ag) complexes. Subsequent treatment of the resulting silver compound with [IrCl(cod)](2) yielded monodentate IrCl(cod)(NHC), which was stable in air. The NHC-Ir complex facilitated efficient asymmetric hydrosilylation of ketones using (EtO)(2)MeSiH under ambient conditions. A chiral ligand containing an isobutyl stereodirecting group was found to be the best ligand for the functionalized NHC-Ir complexes that were examined. A linear relationship was found between the catalyst ee and the product ee. The hydroxy functional group on the NHC ligand side-arm not only induced stereocontrol but also enhanced the reaction rate.

引用

页码：5532 / 5539

页数：8

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