Frustrated Lewis Pairs: Metal-free Hydrogen Activation and More

被引：1712

作者：

Stephan, Douglas W. ^{[1
]}

Erker, Gerhard ^{[2
]}

机构：

[1] Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada

[2] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2010年 / 49卷 / 01期

基金：

加拿大自然科学与工程研究理事会;

关键词：

Lewis acid; Lewis base; hydrogenation; small-molecule activation; steric frustration; HETEROLYTIC DIHYDROGEN ACTIVATION; NONLINEAR-OPTICAL PROPERTIES; FREE CATALYTIC-HYDROGENATION; N-HETEROCYCLIC CARBENES; ASYMMETRIC TRANSFER HYDROGENATION; PHOTOCHEMICAL 2+2 CYCLOADDITION; FUNCTIONAL-GROUP CHEMISTRY; DER-WAALS COMPLEXES; CARBON-DIOXIDE; MOLECULAR-STRUCTURES;

D O I：

10.1002/anie.200903708

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Sterically encumbered Lewis acid and Lewis base combinations do not undergo the ubiquitous neutralization reaction to form "classical" Lewis acid Lewis base adducts. Rather, both the unquenched Lewis acidity and basicity of such sterically "rustrated Lewis pairs (FLPs)"is available to carry out unusual reactions. Typical examples of frustrated Lewis pairs are inter- or intramolecular combinations of bulky phosphines or amines with strongly electrophilic RB(C6F5)2 components. Many examples of such frustrated Lewis pairs are able to cleave dihydrogen heterolytically. The resulting H'/H~ pairs (stabilized for example, in the form of the respective phosphonium cation/hydridoborate anion salts) serve as active metal-free catalysts for the hydrogénation of, for example, bulky imines, enamines, or enol ethers. Frustrated Lewis pairs also react with alheñes, aldehydes, and a variety of other small molecules, including carbon dioxide, in cooperative three-component reactions, offering new strategies for synthetic chemistry. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：46 / 76

页数：31

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