文献类型：期刊文献

英文题名：Pd-Catalyzed Asymmetric Reactions Involving β-Hydride Elimination

作者：Chen, Ziqi[1];Zheng, Qizhi[3];Zhang, Ruinan[4];Fang, Chao[2];Zhang, Pei-Chao[1];Chai, Xiaoyun[1];Zhao, Qingjie[1];Luo, Wenjun[4];Zhao, Jianhong[3];Xu, Bing[1];Zhang, Zhan-Ming[2,5];Zhang, Junliang[2,6,7]

机构：[1]Naval Med Univ, Sch Pharm, Shanghai 200433, Peoples R China;[2]Fudan Univ, Dept Chem, State Key Lab Green Chem Synth & Convers, Shanghai 200438, Peoples R China;[3]East China Univ Sci & Technol, Engn Res Ctr Pharmaceut Proc Chem, Sch Pharm, Minist Educ, Shanghai 200237, Peoples R China;[4]Gannan Normal Univ, Inst Jiangxi Prov Key Lab Synthet Pharmaceut Chem, Coll Chem & Mat Sci, Ganzhou 341000, Jiangxi, Peoples R China;[5]Fudan Zhangjiang Inst, Shanghai 201203, Peoples R China;[6]Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China;[7]Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China

年份：2026

卷号：16

期号：14

起止页码：12858

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20263021143870);Scopus(收录号：2-s2.0-105044828195);WOS:【SCI-EXPANDED(收录号:WOS:001804362800001)】；

基金：We gratefully acknowledge the funding support of the National Key R&D Program of China (No. 2021YFF0701600), NSFC (No. 22031004, 22501294), the Shanghai Municipal Education Commission (No. 20212308) and STCSM (No. 23ZR1445600).

语种：英文

外文关键词：beta-H elimination; palladium catalysis; asymmetric catalysis; enantioselectivity; axial chirality; inherent chirality; central chirality

摘要：beta-hydride (beta-H) elimination is one of the most fundamental elementary reactions in transition metal chemistry, which was discovered by Chugaev and his students in 1899 and later identified by Wilkinson in 1974 as a key mechanism governing the kinetic instability of transition metal alkyl compounds. This reaction is widely involved in various important organic transformations, and its chemoselectivity and regioselectivity have been extensively explored through experiments and theoretical calculations. However, research on the stereoselectivity of beta-H elimination has lagged behind due to the lack of common stereocenters generated during the reaction. In the past decade, rapid progress has been made in the field of asymmetric reactions involving beta-H elimination, where multiple robust and effective strategies have been established for constructing valuable compounds with axial chirality, inherent chirality, or central chirality. Despite these significant advancements, there is still a lack of comprehensive reviews focusing on this specific topic. Herein, we systematically summarize the research advances in palladium-catalyzed asymmetric reactions over the past decade, where beta-H elimination acts as either the enantioselectivity-determining step or the nonenantioselectivity-determining step. For the former, the review is organized around three major reaction categories: desymmetrization-driven asymmetric beta-H elimination, carbene-involved asymmetric beta-H elimination, and Heck reaction-triggered asymmetric beta-H elimination. For the latter, four key reaction types are highlighted, including the asymmetric dearomative Heck reaction, asymmetric aza-Heck reaction, asymmetric Heck reaction, and asymmetric aza-Wacker reaction. We systematically elaborate on the reaction mechanisms, substrate scope, stereochemical control modes, and synthetic applications of these transformations. This review aims to provide valuable insights for medicinal and synthetic organic chemists, serve as a useful reference, inspire innovative reaction design, and promote the further development of this emerging research field.