A Homochiral Metal-Organic Framework as an Effective Asymmetric Catalyst for Cyanohydrin Synthesis

A homochiral metal-organic framework (MOF) of an enantiopure 2,2'-dihydroxy-1,1'-biphenyl ligand was constructed. After exchanging one proton of the dihydroxyl group for Li(I) ions, the framework is shown to be a highly efficient and recyclable heterogeneous catalyst for asymmetric cyanation of aldehydes with up to > 99% ee. Compared with the homogeneous counterpart, the MOF catalyst exhibits significantly enhanced catalytic activity and enantioselectivity, especially at a low catalyst/substrate ratio, due to that the rigid framework could stabilize the catalytically active monolithium salt of biphenol against its free transformation to catalytically inactive and/or less active assemblies in reactions. The synthetic utility of the cyanation was demonstrated in the synthesis of (S)-bufuralol (a nonselective beta-adrenoceptor blocking agent) with 98% ee.