Cofactor-Controlled Regioselective and Enantioselective Hydroformylation

Enantioselective catalysis is one of the central themes for chemical synthesis as for applications, enantiomers are required, especially for pharmaceutical and agrochemical applications. Our group has introduced supramolecular concepts in enantioselective catalysis, including cofactor controlled enantioselective hydrogenation.¹ Herein, we extend this cofactor-controlled catalysis to hydroformylation², which is more challenging as regioselectivity plays a role. An bisphosphite rhodium complex with an integral anion-receptor was prepared. Upon binding small chiral cofactors equipped with an acetate group, specific substrates can be preorganized and converted selectively. We have demonstrated not only enantioselectivity but also regioselectivity can be controlled by chiral-cofactor (only branched product formed, up to 70% ee) in the hydroformylation of vinyl acetate and its derivatives.

References:

1. Reek et al. Am. Chem. Soc. 2011, 133, 17176.
2. Vidal-Ferran et al. Chem. Rev. 2011, 111, 2119.