Ni-Catalyzed Cross Coupling ofAryl Grignard Reagents with Aryl Halides in a Nonpolar Solvent and an Efficient Synthesis of Biaryls Under Neat Conditions  

作　　者：WU Qiang JIN Rizhe KANG Chuanqing CHEN Wenhui BIAN Zheng MA Xiaoye DING Jinying GUO Haiquan QIU Xuepeng GAO Llanxun 

机构地区：[1]State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China [2]University of Chinese Academy of Sciences, Beo'ing 100864, P. R. China

出　　处：《Chemical Research in Chinese Universities》2016年第1期55-61,共7页高等学校化学研究（英文版）

摘　　要：This study details Ni-catalyzed cross coupling of aryl Grignard reagents with aryl halides in toluene, a nonpolar solvent with a high boiling point. The reaction was applied for the synthesis of various biaryls in good yields without the introduction of a large steric ligand. The Kumada-Tamao-Corriu（KTC） reaction in toluene was then successfully modified to proceed under neat conditions for the efficient syntheses of symmetrical biaryls, particularly in large-scale preparations. Unactivated aryl chlorides show higher reactivity than aryl bromides, particularly under neat conditions. Mechanistic investigations suggest a radical procedure for the catalytic cycle, and the origin of the radical intermediates being aryl halides.This study details Ni-catalyzed cross coupling of aryl Grignard reagents with aryl halides in toluene, a nonpolar solvent with a high boiling point. The reaction was applied for the synthesis of various biaryls in good yields without the introduction of a large steric ligand. The Kumada-Tamao-Corriu（KTC） reaction in toluene was then successfully modified to proceed under neat conditions for the efficient syntheses of symmetrical biaryls, particularly in large-scale preparations. Unactivated aryl chlorides show higher reactivity than aryl bromides, particularly under neat conditions. Mechanistic investigations suggest a radical procedure for the catalytic cycle, and the origin of the radical intermediates being aryl halides.

关 键 词：CROSS-COUPLING Nickel BIARYL Reaction mechanism Neat condition 

分 类 号：O643.36[理学—物理化学] O645.12[理学—化学]