化学
电泳剂
表面改性
组合化学
键裂
脱质子化
部分
偶联反应
催化作用
烷基化
亲电芳香族取代
立体化学
有机化学
离子
物理化学
作者
Francisco de Azambuja,Ming‐Hsiu Yang,Taisiia Feoktistova,Manikandan Selvaraju,Alexander C. Brueckner,Markas A. Grove,Suvajit Koley,Paul Ha‐Yeon Cheong,Ryan A. Altman
出处
期刊:Nature Chemistry
[Nature Portfolio]
日期:2020-03-09
卷期号:12 (5): 489-496
被引量:47
标识
DOI:10.1038/s41557-020-0428-1
摘要
Transition metal-catalysed C-H functionalization and decarboxylative coupling are two of the most notable synthetic strategies developed in the past 30 years. Here, we connect these two reaction pathways using bases and a simple Pd-based catalyst system to promote a para-selective C-H functionalization reaction from benzylic electrophiles. Experimental and computational mechanistic studies suggest a pathway that involves an uncommon Pd-catalysed dearomatization of the benzyl moiety followed by a base-enabled rearomatization through a formal 1,5-hydrogen migration. This reaction complements 'C-H activation' strategies that convert inert C-H bonds into C-metal bonds prior to C-C bond formation. Instead, this reaction exploits an inverted sequence and promotes C-C bond formation prior to deprotonation. These studies provide an opportunity to develop general para-selective C-H functionalization reactions from benzylic electrophiles and show how new reactive modalities may be accessed with careful control of the reaction conditions.
科研通智能强力驱动
Strongly Powered by AbleSci AI