Asymmetric Palladium-Catalyzed Allylic Alkylation Using Dialkylzinc Reagents: A Remarkable Ligand Effect

Authors


  • We are grateful to the University of Vienna and the Max-Planck-Society for support. This work was financed by the DFG (MA 4861/3-1 and MA4681/3-2) and the ERC (StG FLATOUT to N.M.). We thank Prof. H. G. Schmalz (University of Cologne) for the generous donation of chemicals. Some of this research was carried out in the Max-Planck-Institut für Kohlenforschung, which we acknowledge gratefully.

Abstract

A serendipitously discovered palladium-catalyzed asymmetric allylic alkylation reaction with diorganozinc reagents, which displays broad functional group compatibility, is reported. This novel transformation hinges on a remarkable ligand effect which overrides the standard “umpolung” reactivity of allyl–palladium intermediates in the presence of dialkylzincs. Owing to its mild conditions, enantioselective allylic alkylations of racemic allylic electrophiles are possible in the presence of sensitive functional groups.

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