东华大学谢伟龙团队报道了非活化仲、伯烷基卤化物与芳基硼交偶联的通用铜催化体系。相关研究成果于2023年12月12日发表于国际顶尖学术期刊《美国化学会杂志》上。

Suzuki–Miyaura交叉联偶联（SMC）是构建碳-碳键的强大工具。然而，sp3杂化的烷基卤化物与芳基硼的偶联经常遇到几个问题，如烷基卤化物的缓慢氧化加成和金属-烷基物种的竞争性β-氢化物消除副途径。在先前的报道中，铜主要用于sp2芳基卤化物的偶联，而与未活化的烷基卤化物的交叉偶联的报道要少得多。

该文中，研究人员证明了高效铜体系能够使芳基溴与各种未活化的仲和伯烷基卤化物偶联，包括溴化物、碘化物，甚至强大的氯化物。该系统具有范围广、功能容错性好、可扩展性强、实用性强等特点。此外，目前的系统可以以中到高效率应用于复杂分子的后期功能化。

附：英文原文

Title: A General Copper Catalytic System for Suzuki–Miyaura Cross-Coupling of Unactivated Secondary and Primary Alkyl Halides with Arylborons

Author: Yonglei Zhou, Liping Qiu, Jian Li, Weilong Xie

Issue&Volume: December 12, 2023

Abstract: Suzuki–Miyaura cross-couplings (SMC) are powerful tools for the construction of carbon–carbon bonds. However, the couplings of sp3-hybridized alkyl halides with arylborons often encounter several problematic issues such as sluggish oxidation addition of alkyl halides and competitive β-hydride elimination side pathways of metal–alkyl species. In  precedent reports, copper is mainly utilized for the coupling of sp2-aryl halides, and the cross-couplings with unactivated alkyl halides are far less reported. Herein, we demonstrate that a high-efficiency copper system enabled the coupling of arylborons with various unactivated secondary and primary alkyl halides including bromides, iodides, and even robust chlorides. The present system features broad scope, excellent functionality tolerance, scalability, and practicality. Moreover, the current system could be applied for the late-stage functionalization of complex molecules in moderate to high efficiency.

DOI: 10.1021/jacs.3c10628

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.3c10628