Organo-f-element catalysts for efficient and highly selective hydroalkoxylation and hydrothiolation

Abstract

Lanthanide and actinide catalysts have made significant contributions to many areas of homogeneous catalysis with hydroelementation of C–C unsaturation being a notable area of success. In this Perspective, we review recent advances in f-element hydroelementation for highly selective hydroalkoxylation and hydrothiolation processes. As will be discussed, f-element hydroalkoxylation and hydrothiolation catalysts exhibit selectivities unobtainable by many late transition metal complexes. First, we review lanthanide-mediated hydroalkoxylation processes with mechanistic, thermodynamic, and kinetic considerations discussed, and then compare/contrast them with analogous C–N and C–P bond-forming transformations. In addition, computational studies are discussed which provide further insight into this transformation and the observed selectivities. Next, actinide-mediated alkyne hydrothiolation is reviewed with a similar discussion of reactivity, mechanism, and thermodynamics.