Lanthanide Pybox Complexes as Catalysts for Enantioselective Silylcyanation of Aldehydes

Abstract

Complexes of lanthanide chlorides with pybox ligands catalyze the enantioselective silylcyanation of aromatic and aliphatic aldehydes with ee's of up to 91% under mild and convenient conditions. Studies of catalysts prepared with pybox ligands of varying enantiomeric purity show no marked nonlinear effects, indicating a monometallic transition state. A mechanism for the catalytic reaction is proposed. Crystal structures of [LnCl2(S-Pri-pybox)2][LnCl4(S-Pri-pybox)] (Ln = Eu, Yb) are reported. The structure of the related triflate complex [La(OTf)3(S-Pri-pybox)2] is also reported. Diastereoselectivity has been observed in the reactions of Ln(OTf)3 with racemic Pri-pybox: for Ln = Eu, a heterochiral product containing one R- and one S-pybox ligand is observed, whereas for Ln = Yb a racemic mixture of homochiral bis(pybox) complexes is formed.