The synthesis and efficient one-pot catalytic "self-breeding" of asymmetrical NC(sp(3))E-hybridised pincer complexes.

Cyclopalladation of the pyridyl-substituted chiral phosphine sulfide (N-P=S) and oxide (N-P=O) compounds afforded the asymmetric N-C(sp(3))*-S and N-C(sp(3))*-O pincer complexes. When applied as catalysts in asymmetric hydrophosphination, the newly developed aliphatic pincer catalyst could be recycled over three runs and obtained in large quantities via a one-pot "self-breeding" catalytic protocol.