Palladium pincer-complexes readily catalyze the formation of allylstannanes, allenylstannanes/silanes and allylboronates from easily available allylic and propargylic substrates and dimetallic reagents. The catalytic activity and selectivity of the pincer-complexes can efficiently be fine-tuned by changing the heteroatoms in the side arms. Pincer-complexes with nitrogen, sulfur and selenium atoms in the side arms are very efficient for creating C–Sn, C–Si and C–B bonds, while phosphorus based complexes can be employed for catalytic cleavage of C–Sn and C–B bonds. Most of the catalytic metallation (stannylation and borylation) processes can easily be combined with other reactions, and thus one-pot procedures can be designed for the synthesis of homoallylic alcohols, homoallylic amines and α-amino acids from simple precursors.