南开大学资伟伟团队报道了Pd/Cu催化1,3-丁二烯的对映选择性三组分光化学1,4-双烷基化反应。相关研究成果发表在2022年6月27日出版的《德国应用化学》。
激发态钯催化已成为一个活跃的研究领域，但控制对映选择性仍然是一个挑战。
该文中，研究人员报告了首个使用协同钯/铜催化来完成1,3-丁二烯的三组分光化学1,4-双烷基化反应。因此，从三种简单的起始材料，烷基溴、丁二烯和醛亚胺酯快速合成了带有四元立体中心的α-氨基酸酯。对反应机理的实验和计算研究证实了一个自由基途径，该途径涉及激发态钯物种的催化作用。立体化学主要由手性铜催化剂控制。
附：英文原文
Title: Enantioselective Three-Component Photochemical 1,4-Bisalkylation of 1,3-Butadiene with Pd/Cu Catalysis
Author: Huimin Yu, Qinglong Zhang, Weiwei Zi
Issue&Volume: 2022-06-27
Abstract: Catalysis by excited-state palladium has emerged as an active area of research, but controlling the enantioselectivity remains a challenge. Herein, we report the use of synergistic Pd/Cu catalysis to accomplish the first three-component photochemical 1,4-bisalkylation reactions of 1,3-butadiene. Consequently, α-amino acid esters bearing quaternary stereocenters were expeditiously synthesized from three simple starting materials: an alkyl bromide, butadiene, and an aldimine ester. Experimental and computational investigation of the reaction mechanism confirmed a radical pathway involving catalysis by an excited-state palladium species. The stereochemistry is mainly controlled by the chiral Cu catalyst.
DOI: 10.1002/anie.202208411
Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202208411
