Zhen Hu, Dushyant Singh, Bruce A. Arndtsen
We describe a versatile method for using earth-abundant nickel catalysts in carbonylative coupling reactions. In this process, the wavelength-dependent excitation of a Xantphos-ligated nickel in concert with a weakly nucleophilic fluoride anion offers a route to build up acyl fluorides in high yield from classically unreactive C(sp 3 ) bromides. Coupling the formation of the acyl fluorides with subsequent nucleophilic addition can be used to construct a diverse array of amides, esters, and thioesters via carbonylations.