Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas , Avenida Los Naranjos s/n, 46022 Valencia, Spain.
Chem Rev. 2018 Feb 28;118(4):1410-1459. doi: 10.1021/acs.chemrev.7b00340. Epub 2018 Jan 10.
The borrowing hydrogen (BH) principle, also called hydrogen auto-transfer, is a powerful approach which combines transfer hydrogenation (avoiding the direct use of molecular hydrogen) with one or more intermediate reactions to synthesize more complex molecules without the need for tedious separation or isolation processes. The strategy which usually relies on three steps, (i) dehydrogenation, (ii) intermediate reaction, and (iii) hydrogenation, is an excellent and well-recognized process from the synthetic, economic, and environmental point of view. In this context, the objective of the present review is to give a global overview on the topic starting from those contributions published prior to the emergence of the BH concept to the most recent and current research under the term of BH catalysis. Two main subareas of the topic (homogeneous and heterogeneous catalysis) have been identified, from which three subheadings based on the source of the electrophile (alkanes, alcohols, and amines) have been considered. Then the type of bond being formed (carbon-carbon and carbon heteroatom) has been taken into account to end-up with the intermediate reaction working in tandem with the metal-catalyzed hydrogenation/dehydrogenation step. The review has been completed with the more recent advances in asymmetric catalysis using the BH strategy.
borrowing hydrogen (BH) 原理,也称为氢自动转移,是一种强大的方法,它将转移氢化(避免直接使用氢气)与一个或多个中间反应结合起来,合成更复杂的分子,而不需要繁琐的分离或隔离过程。该策略通常依赖于三个步骤:(i)脱氢,(ii)中间反应,和(iii)加氢,从合成、经济和环境的角度来看,这是一个极好的、公认的过程。在这种情况下,本综述的目的是从 BH 概念出现之前发表的那些贡献开始,对该主题进行全面概述,直到最近和当前的 BH 催化研究。该主题有两个主要的子领域(均相和多相催化),其中三个小标题基于亲电体的来源(烷烃、醇和胺)进行了考虑。然后考虑了正在形成的键的类型(碳-碳和碳杂原子),最后是与金属催化的加氢/脱氢步骤协同工作的中间反应。综述中还包括了使用 BH 策略在不对称催化方面的最新进展。