Development of nickel-catalyzed asymmetric reductive cross-couplings

Cross-coupling reactions have emerged as powerful methods to form carbon-carbon and carbon-heteroatom bonds in a vast array of synthetic contexts. Nickel-catalyzed reductive cross-coupling reactions have opened up a new mode of reactivity, allowing for the cross-coupling of bench-stable electrophiles as both coupling partners. Asym. variants, which proceed with the use of a chiral ligand, increase mol. complexity by introducing newly formed stereocenters with high levels of enantioselectivity. Application of this methodol. to a wide array of electrophiles has led to the development of a no. of asym. transformations incorporating both C(sp2)-hybridized electrophiles (aryl iodides, alkenyl bromides, and acyl chlorides) and C(sp3)-hybridized electrophiles (benzyl chlorides and α-chloronitriles). Here we will discuss our most recent efforts in the development and application of these cross-coupling reactions.