Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
Angew Chem Int Ed Engl. 2017 Feb 1;56(6):1581-1585. doi: 10.1002/anie.201609635. Epub 2016 Dec 29.
While chemoselectivities in Pd -catalyzed coupling reactions are frequently non-intuitive and a result of a complex interplay of ligand/catalyst, substrate, and reaction conditions, we herein report a general method based on Pd that allows for an a priori predictable chemoselective Csp2 -Csp2 coupling at C-Br in preference to C-OTf and C-Cl bonds, regardless of the electronic or steric bias of the substrate. The C-C bond formations are extremely rapid (<5 min at RT) and are catalyzed by an air- and moisture-stable Pd dimer under open-flask conditions.
虽然钯催化偶联反应的化学选择性通常是不可预测的，是配体/催化剂、底物和反应条件复杂相互作用的结果，但我们在此报告了一种基于钯的通用方法，该方法可以预先预测 Csp2-Csp2 偶联在 C-Br 上的化学选择性，而不是 C-OTf 和 C-Cl 键，无论底物的电子或空间位阻如何。C-C 键的形成非常迅速（在 RT 下 <5 min），并且在开放瓶条件下由空气和水分稳定的钯二聚体催化。
