The reaction of the P*-chiral bicyclophosphoramidite 1 with [Pd(allyl)Cl₂] (ligand / Pd molar ratio = 2/1) in wet CD₂Cl₂ in situ leads to the formation of the mixed ligand complex 2. In this case, autocatalytic hydrolysis of one of two coordinated ligands and its deprotonation occurs. In turn, the allylic ligand is protonated to form a propene molecule. Complex 2 can be obtained by the reaction of 1 with [Pd(allyl)Cl₂] (ligand / Pd molar ratio = 1 /1) and further addition of dialkyl phosphite 4 to the intermediate complex 3 (Scheme 1).

Bicyclophosphoramidite 1 as a precursor-ligand provides up to 68% ee in the Pd-catalyzed asymmetric allylic substitution reactions (Scheme 2).

This work was supported by the Russian Science Foundation (Project № 23-73-01172).