Decarboxylative Cross-Coupling Enabled by Fe and Ni Metallaphotoredox Catalysis

Abstract

Decarboxylative cross-coupling of carboxylic acids and aryl halides has become a key transformation in organic synthesis to form C(sp²)–C(sp³) bonds. In this report, a base metal pairing between Fe and Ni has been developed with complementary reactivity to the well-established Ir and Ni metallaphotoredox reactions. Utilizing an inexpensive FeCl₃ cocatalyst along with a pyridine carboxamidine Ni catalyst, a range of aryl iodides can be preferentially coupled to carboxylic acids over boronic acid esters, triflates, chlorides, and even bromides in high yields. Additionally, carboxylic acid derivatives containing heterocycles, N-protected amino acids, and protic functionality can be coupled in 23–96% yield with a range of sterically hindered, electron-rich, and electron-deficient aryl iodides. Preliminary catalytic and stoichiometric reactions support a mechanism in which Fe is responsible for the activation of carboxylic acid upon irradiation with light and a Ni^I alkyl intermediate is responsible for activation of the aryl iodide coupling partner followed by reductive elimination to generate product.