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

共 83 条

[11] Iridium complex bearing a chiral hydroxy-amide functionalized N-heterocyclic carbene: a catalyst precursor for asymmetric transfer hydrogenation [J].

Chiyojima, Hiroyuki ;

Sakaguchi, Satoshi .

TETRAHEDRON LETTERS, 2011, 52 (50) :6788-6791

[12]

Diez-Gonzalez S., 2011, N HETEROCYCLIC CARBE

[13] Copper, silver, and gold complexes in hydrosilylation reactions [J].

Diez-Gonzalez, Silvia ;

Nolan, Steven P. .

ACCOUNTS OF CHEMICAL RESEARCH, 2008, 41 (02) :349-358

[14] N-Heterocyclic Carbenes in Late Transition Metal Catalysis [J].

Diez-Gonzalez, Silvia ;

Marion, Nicolas ;

Nolan, Steven P. .

CHEMICAL REVIEWS, 2009, 109 (08) :3612-3676

[15] Functionalized N-Heterocyclic Carbene Ligands for Dual Enantioselective Control in the Cu-Catalyzed Conjugate Addition of Dialkylzinc Compounds to Acyclic Enones [J].

Dohi, Kenta ;

Kondo, Junko ;

Yamada, Haruka ;

Arakawa, Ryuichi ;

Sakaguchi, Satoshi .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2012, 2012 (36) :7143-7152

[16] Metal-mediated asymmetric alkylation using chiral N-heterocyclic carbenes derived from chiral amines [J].

Douthwaite, Richard E. .

COORDINATION CHEMISTRY REVIEWS, 2007, 251 (5-6) :702-717

[17] Synthesis of novel axially chiral Rh-NHC complexes derived from BINAM and application in the enantioselective hydrosilylation of methyl ketones [J].

Duan, WL ;

Shi, M ;

Rong, GB .

CHEMICAL COMMUNICATIONS, 2003, (23) :2916-2917

[18]

Enders D, 1998, EUR J INORG CHEM, P913

[19] Synthesis of chiral triazolinylidene and imidazolinylidene transition metal complexes and first application in asymmetric catalysis [J].

Enders, D ;

Gielen, H .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2001, 617 (01) :70-80

[20] Catalytic asymmetric hydrosilylation with (triazolinylidene)rhodium complexes containing an axis of chirality [J].

Enders, D ;

Gielen, H ;

Breuer, K .

TETRAHEDRON-ASYMMETRY, 1997, 8 (21) :3571-3574

← 1 2 3 4 5 6 7 8 9 →