Photoredox-Assisted Reductive Cross-Coupling: Mechanistic Insight into Catalytic Aryl-Alkyl Cross-Couplings

Here, we describe a photoredox-assisted catalytic system for the direct reductive coupling of two carbon electrophiles. Recent advances have shown that nickel catalysts are active toward the coupling of sp(3)-carbon electrophiles and that well-controlled, light-driven coupling systems are possible. Our system, composed of a nickel catalyst, an iridium photosensitizer, and an amine electron donor, is capable of coupling halocarbons with high yields. Spectroscopic studies support a mechanism where under visible light irradiation the Ir photosensitizer in conjunction with triethanolamine are capable of reducing a nickel catalyst and activating the catalyst toward cross coupling of carbon electrophiles. The synthetic methodology developed here operates at low 1 mol % catalyst and photosensitizer loadings. The catalytic system also operates without reaction additives such as inorganic salts or bases. A general and effective sp(2)-sp(3) cross-coupling scheme has been achieved that exhibits tolerance to a wide array of functional groups.