Harnessing a Tripyridyl Ligand in Zirconaaziridine-Mediated Ni-Catalyzed Cross-Electrophile Couplings

High Resolution Image Download MS PowerPoint Slide Cross-electrophile coupling of two distinct organic halides has emerged as a powerful strategy for expanding chemical spaces. In this context, stereoselective nickel catalysis holds high synthetic value, yet remains relatively underdeveloped.. Herein, we report a zirconaaziridine-mediated cross-electrophile coupling protocol catalyzed by a tripyridyl-ligated nickel complex, enabling the diastereoselective synthesis of substituted cyclohexyl, tetrahydropyranyl, and piperidyl scaffolds with high levels of stereocontrol and broad functional group tolerance. Experimental investigations including kinetic and computational studies support a “sequential reduction” mechanism, wherein redox-transmetalation between a Ni(II) dihalide complex and zirconaaziridine is proposed to generate a monovalent Ni(I) halide species alongside a Cp 2 Zr(III) intermediate that facilitates the conversion of an alkyl iodide into the corresponding C(sp 3 ) radical.