Nickel- and Palladium-Catalyzed Cross-Coupling of Stibines with Organic Halides: Site-Selective Sequential Reactions with Polyhalogenated Arenes
Dejiang Zhang, Ting Tang, Zhao Zhang, Liyuan Le, Zhi Xu, Lu Hao, Tong Zhou, Dishu Zeng, Wai‐Yeung Wong, Shuang‐Feng Yin, Arash Ghaderi, Nobuaki Kambe, Renhua Qiu
Abstract
Herein, we disclose a general and efficient method for the synthesis of Sb-aryl and Sb-alkyl stibines by the nickel-catalyzed cross-coupling of halostibines with organic halides. The synthesized Sb-aryl stibines couple with aryl halides to give biaryls efficiently via palladium catalysis. Sequential reactions of stibines with polyhalogenated arenes bearing active C–I/C–Br sites and inactive C–Cl sites successfully proceeded, resulting in the formation of a variety of complex molecules with good site selectivity. Drugs such as diflunisal and fenbufen, as well as a fenofibrate derivative, were synthesized on gram scales in good yields, together with the high recovery of chlorostibine. Furthermore, catalytic mechanisms are proposed based on the results of control experiments.