Nickel-Catalyzed Stille Cross Coupling of C-O Electrophiles

Aryl sulfamates, tosylates, and mesylates undergo efficient Ni-catalyzed cross coupling with diverse organostannanes in the presence of relatively unhindered alkylphosphine ligands and KF. The coupling is valuable for difficult bond constructions, such as aryl- heteroaryl, aryl-alkenyl, and aryl-alkynyl, using non-triflate phenol derivatives. A combination of experimental and computational studies implicate an unusual mechanism for transmetalation involving an 8-centered cyclic transition state. This reaction is inhibited by chloride sources due to slow transmetalation of organostannanes at a Ni(II)-chloride intermediate. These studies help to explain why prior efforts to achieve Ni-catalyzed Stille coupling of phenol derivatives were unsuccessful.