Zhou Yonglei, Qiu Liping, Li Jian, Xie Weilong
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Key Laboratory of Science and Technology of Eco-Textile, Ministry of Education, College of Chemistry and Chemical Engineering, Donghua University, Shanghai 201620, China.
J Am Chem Soc. 2023 Dec 27;145(51):28146-28155. doi: 10.1021/jacs.3c10628. Epub 2023 Dec 12.
Suzuki-Miyaura cross-couplings (SMC) are powerful tools for the construction of carbon-carbon bonds. However, the couplings of sp-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 sp-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.
铃木-宫浦交叉偶联反应（SMC）是构建碳-碳键的有力工具。然而，sp杂化的卤代烃与芳基硼酸的偶联反应常常会遇到一些问题，如卤代烃的氧化加成反应缓慢以及金属烷基物种竞争性的β-氢消除副反应途径。在之前的报道中，铜主要用于sp芳基卤化物的偶联反应，而与未活化卤代烃的交叉偶联反应报道较少。在此，我们证明了一种高效的铜体系能够实现芳基硼酸与各种未活化的仲卤代烃和伯卤代烃（包括溴化物、碘化物，甚至是稳定性高的氯化物）的偶联反应。该体系具有适用范围广、官能团耐受性好、可扩展性和实用性强等特点。此外，当前体系能够以中等到高效率应用于复杂分子的后期官能团化反应。
