Palladium Catalytic Species Containing Chiral Phosphites: Towards a Discrimination between Molecular and Colloidal Catalysts

Palladium nanoparticles ( Pd1 – Pd3 ) stabilized by chiral diphosphite ligands ( 1 – 3 ), were synthesized and tested as catalysts for the allylic alkylation reaction, using different substrates ( rac ‐ I , rac ‐ III and rac ‐ V ). Carbohydrate ligands ( 1 and 2 ), only differing in the C‐3 configuration, led to a remarkable difference in stability of the corresponding nanoparticles: while Pd1 is a robust catalyst, Pd2 decomposes into molecular species. In addition, the high enantioselective systems, Pd1 and Pd3 , are only active for a substrate containing phenyl groups. Concerning the catalytic behaviour of the corresponding molecular systems, palladium complexes coordinated to ligands 1 or 3 , gave excellent asymmetric inductions, but an analogous catalyst accommodating ligand 2 , was not found selective.