Nickel- and Palladium-Catalyzed Cross-Coupling of Stibines with Organic Halides: Site-Selective Sequential Reactions with Polyhalogenated Arenes

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.