Synthesis, coordination properties and application of new N,N-ligands based on bornyl and binaphthylazepine chiral backbones in palladium-catalyzed allylic substitution reactions

摘要

The synthesis of new imine-amine and diamine ligands, based on both the atropisomeric (Sa)- or (Ra)-1,1′-binaphthyl and (R)-bornyl backbones, and incorporating an ethylenediamino spacer, are reported. In addition, analogue ligands in which one chiral arm is replaced by the achiral NMe2 group were synthesized. These N,N-ligands when coordinated to a palladium metal centre form highly enantioselective catalysts for the asymmetric allylic alkylation of rac-2-acetoxy-1,3-diphenylpropene by dimethyl malonate. In one case, the synergic effect of the chirality elements in the palladium catalyst afforded the (S) substitution product with an enantiomeric excess (ee) of >99 %. Based on NMR studies of the active species in solution, a reliable explanation for the origin of the enantioselectivity of these palladium catalysts is also provided. New dinitrogen chiral ligands were synthesized and investigated in palladium-catalyzed allylic alkylation reactions. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.