Amine Nucleophiles

About

Background: Use of a titanium-containing phosphinoamide complex to generate a reactive Pd-Ti heterobimetallic catalyst. It has been established that Pd- Ti heterobimetallic complexes are efficient catalysts for allylic aminations and for the first time enable catalysis with hindered secondary amine nucleophiles at room temperature. In addition, a variety of titanium-containing ligand structures were shown to enable room temperature catalysis with hindered amines, presumably via in situ formation of an electron-withdrawing M- M dative interaction. These catalysts are efficient for a range of hindered amine nucleophiles, including for the formation of pyrrolidines and piperidines via intramolecular aminations. These results confirm the potential of bimetallic complexes to enable catalysis that is currently unachievable with monometallic catalysts and suggest that heterobimetallic complexes could find application more broadly in organic synthesis. Continuing efforts in our laboratory are aimed at understanding and quantifying the catalytic potential of the M-M interaction in these complexes and the ability of this interaction to expand reactivity in a variety of transition-metal-catalyzed processes.   About the Market: General reaction procedures and characterization data for all new compounds is available free of charge via the internet at http://pubs.acs.org.