Mild and Selective H/D Exchange at the β Position of Aromatic α-Olefins by N-Heterocyclic Carbene-Hydride-Rhodium Catalysts

被引：65

作者：

Di Giuseppe, Andrea ^{[1
,2
]}

Castarlenas, Ricardo ^{[1
]}

Perez-Torrente, Jesus J. ^{[1
]}

Lahoz, Fernando J. ^{[1
]}

Polo, Victor ^{[3
]}

Oro, Luis A. ^{[1
]}

机构：

[1] Univ Zaragoza, Inst Univ Catalisis Homogenea, Inst Ciencia Mat Aragon, CSIC, E-50009 Zaragoza, Spain

[2] Univ Aquila, Dipartimento Chim Ingn Chim & Mat, I-67100 Coppito, AQ, Italy

[3] Univ Zaragoza, Dept Quim Fis, E-50009 Zaragoza, Spain

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2011年 / 50卷 / 17期

关键词：

H/D exchange; hydride ligands; N-heterocyclic carbene; rhodium; steric induction; C-H ACTIVATION; IRIDIUM(I) COMPLEXES; DEUTERIUM-OXIDE; LIGANDS; PALLADIUM; BOND; ISOMERIZATION; HYDROCARBONS; DEUTERATION; OXIDATION;

D O I：

10.1002/anie.201007238

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Pacman bites selectively! Stable rhodium(III)-N-heterocyclic carbene-hydride complexes (Pacman-like catalysts) are highly active and selective catalysts for H/D exchange at the β position of aromatic α-olefins (see picture). The interplay between bulky N-heterocyclic carbene and quinolinate ligands determines the size of the steric window responsible for this selectivity. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：3938 / 3942

页数：5

共 50 条

[1]

[Anonymous], 2005, ANGEW CHEM

[2] Fused polycyclic nucleophilic carbenes - synthesis, structure, and function [J].

Arduengo, Anthony J., III ;

Iconaru, Luigi I. .

DALTON TRANSACTIONS, 2009, (35) :6903-6914

[3]

Atzrodt J., 2007, ANGEW CHEM, V119, P7890

[4] The renaissance of H/D exchange [J].

Atzrodt, Jens ;

Derdau, Volker ;

Fey, Thorsten ;

Zimmermann, Jochen .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (41) :7744-7765

[5] Highly active iridium(I) complexes for catalytic hydrogen isotope exchange [J].

Brown, Jack A. ;

Irvine, Stephanie ;

Kennedy, Alan R. ;

Kerr, William J. ;

Andersson, Shalini ;

Nilsson, Goeran N. .

CHEMICAL COMMUNICATIONS, 2008, (09) :1115-1117

[6] PLATINUM-CATALYZED EXCHANGE OF AROMATIC COMPOUNDS WITH DEUTERIUM OXIDE [J].

BROWN, WG ;

GARNETT, JL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (19) :5272-5274

[7] A predictably selective aliphatic C-H oxidation reaction for complex molecule synthesis [J].

Chen, Mark S. ;

White, M. Christina .

SCIENCE, 2007, 318 (5851) :783-787

[8] Chelation-assisted rhodium hydride-catalyzed regioselective H/D exchange in arenes [J].

Chen, Shanshan ;

Song, Guoyong ;

Li, Xingwei .

TETRAHEDRON LETTERS, 2008, 49 (48) :6929-6932

[9] Flexible, Bowl-Shaped N-Heterocyclic Carbene Ligands: Substrate Specificity in Iridium-Catalyzed Ketone Hydrosilylation [J].

Chianese, Anthony R. ;

Mo, Allen ;

Datta, Dibyadeep .

ORGANOMETALLICS, 2009, 28 (02) :465-472

[10] Cyclopentadienyl and olefin substituent effects on insertion and β-hydrogen elimination with group 4 metallocenes.: Kinetics, mechanism, and thermodynamics for zirconocene and hafnocene alkyl hydride derivatives [J].

Chirik, PJ ;

Bercaw, JE .

ORGANOMETALLICS, 2005, 24 (22) :5407-5423

← 1 2 3 4 5 →