西湖大学Hang Shi课题组的最新研究利用铑催化实现了烷基芳烃与迈克尔受体的苄基加成反应。相关论文发表在2022年6月29日出版的《德国应用化学》杂志上。
在该文中，课题组报道了铑催化的烷基芳烃与迈克尔受体的苄基加成反应，以形成C(sp3)-C (sp3)键。该催化剂被认为可通过η-6配位活化芳香环，在无碱的情况下，显著促进未活化苄基C-H键的去质子化和生成的碳负离子向α,β-不饱和双键加成。值得注意的是，通过发展配体，这种无副产物的方法提供了一种获得全碳季碳中心的途径。
据介绍，在苄基加成中用烷基芳烃作为亲核前体具有挑战性，因为这些化合物的苄基氢原子对去质子化是惰性的。
附：英文原文
Title: Rhodium-Catalyzed Benzylic Addition Reactions of Alkylarenes to Michael Acceptors
Author: Yuntong Li, Wen-Qiang Wu, Hui Zhu, Qi-Kai Kang, Lun Xu, Hang Shi
Issue&Volume: 2022-06-29
Abstract: The use of alkylarenes as nucleophile precursors in benzylic addition is challenging because the benzylic hydrogen atoms of these compounds are inert to deprotonation. Herein, we report Rh-catalyzed benzylic addition of alkylarenes to Michael acceptors for the formation of C(sp3)–C(sp3) bonds. The catalyst is proposed to activate the aromatic ring via η6-coordination, dramatically facilitating deprotonation of the unactivated benzylic C–H bond and addition of the resulting carbanion to the α,β-unsaturated double bond in the absence of bases. Notably, this byproduct-free method provides an access to all-carbon quaternary centers through the development of ligands.
DOI: 10.1002/anie.202207917
Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202207917
