“受阻路易斯酸碱对”催化的不对称氢化反应

doi:10.6023/A14040344

摘要/Abstract

不对称催化氢化反应在有机合成化学中占有重要地位，是获得光学活性化合物最有效的手段之一. 近五十年，过渡金属催化的不对称氢化反应得到了快速发展，取得了令人瞩目的成就. 相对而言，非金属催化不对称氢化研究刚刚起步，面临着诸多挑战性难题. “受阻路易斯酸碱对”是由大位阻路易斯酸和路易斯碱组成，由于位阻因素，它们不能形成传统的路易斯酸碱加合物，从而表现出一些特殊的性质和反应活性. 自2006年Stephan小组首次发现“受阻路易斯酸碱对”可逆活化氢气以来，它在氢气，二氧化碳，一氧化氮等小分子活化及催化氢化方面得到了广泛应用. 同时，也为非金属催化的不对称氢化反应提供了难得的机遇，并取得了一些重要研究进展. 本文从手性底物诱导和手性催化剂控制两方面介绍“受阻路易斯酸碱对”在不对称氢化反应中的研究成果，并对这一新兴领域未来的发展进行展望.

关键词: 受阻路易斯酸碱对, 不对称氢化, 非金属催化剂, 手性硼烷

Catalytic asymmetric hydrogenation of unsaturated substrates is one of the most important transformations in organic chemistry, which provides a significant approach to produce optically active compounds both in academia and chemical industry due to its atom-economy and high efficiency. Since the original work of Knowles and Sabacky in 1960s, transition-metal-catalyzed asymmetric hydrogenation has been well developed with great achievements. However, metal-free asymmetric hydrogenation utilizing molecular hydrogen is extremely challenging, and has long been an unsolved problem. Frustrated Lewis pairs (FLPs) with a combination of sterically encumbered Lewis acids and Lewis bases preclude the formation of classical Lewis acid-base adducts via dative bonds due to the steric effects, and they therefore possess novel and interesting properties and reactivities. Since frustrated Lewis pairs was first disclosed to enable heterolytic cleavage of H₂ reversibly by Stephan and co-workers in 2006, its applications on activating various of small molecules such as H₂, CO₂, NO and catalytic hydrogenation of unsaturated compounds were reported. Asymmetric hydrogenation under H₂ by metal-free catalysts has been realized and has witnessed important progress. In this perspective, the achievements on frustrated Lewis pair catalyzed asymmetric hydrogenation are discussed from two aspects: (1) asymmetric hydrogenation induced by chiral substrates; (2) asymmetric hydrogenation catalyzed by chiral frustrated Lewis pairs.

Key words: frustrated Lewis pairs, asymmetric hydrogenation, metal-free catalysts, chiral borane

引用此文

刘勇兵, 杜海峰. “受阻路易斯酸碱对”催化的不对称氢化反应[J]. 化学学报, 2014, 72(7): 771-777.

Liu Yongbing, Du Haifeng. Frustrated Lewis Pair Catalyzed Asymmetric Hydrogenation[J]. Acta Chimica Sinica, 2014, 72(7): 771-777.

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