Organo-f-element catalysts for efficient and highly selective hydroalkoxylation and hydrothiolation.
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.
Weiss
Charles J
CJ
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA.
Marks
Tobin J
TJ
D000480:Alkynes / Q000737:chemistry; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008958:Models, Molecular; D013438:Sulfhydryl Compounds / Q000737:chemistry; D028561:Transition Elements / Q000737:chemistry*
D000480:Alkynes; D056831:Coordination Complexes; D028581:Lanthanoid Series Elements; D013438:Sulfhydryl Compounds; D028561:Transition Elements