Dabbling with air-stable organoaluminum species

被引：26

作者：

Biswas, K ^{[1
]}

Chapron, A ^{[1
]}

Cooper, T ^{[1
]}

Fraser, PK ^{[1
]}

Novak, A ^{[1
]}

Prieto, O ^{[1
]}

Woodward, S ^{[1
]}

机构：

[1] Univ Nottingham, Sch Chem, Nottingham NG7 2RD, England

来源：

PURE AND APPLIED CHEMISTRY | 2006年 / 78卷 / 02期

关键词：

1,2-additions; stereoselective; DABCO(AlMe3)(2); trimethylaluminum; catalytic asymmetric synthesis; asymmetric synthesis;

D O I：

10.1351/pac200678020511

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Highly stereoselective 1,2-additions of AlMe3 or its air-stable analog DABCO(AlMe3)(2) to aldehydes are realized in the presence of a Ni(acac)(2)-derived catalyst using phosphoramidite ligands giving sec-alcohols in up to 95 % ee. Very high turnover number (TON) (>1500) and turnover frequency (TOF) (>350 h(-1)) values can be realized in these reactions. The substrate range, trials of various (DABCO)(a)(AlR3)(b) reagents (a = 0.1; b = 1.2; R = Me, Et, Bu-i), ligands, and molecular modeling studies are used to propose a working model for the catalytic cycle and the origin of the stereo selectivity. The phosphoramidite ligand is proposed to bind the nickel in an eta(2) manner via the P-donor and one of the C=C aryl bonds of the CHAr amine group. Preliminary studies indicate that DABCO(AlMe3)(2) can also be used as a methyl source in Pd-catalyzed cross-coupling reactions of ArX (X = Br, I) species.

引用

页码：511 / 518

页数：8

共 21 条

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