The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions.

We have designed the first chiral diene-based metal-organic framework (MOF), E-MOF, and postsynthetically metalated E-MOF with Rh(i) complexes to afford highly active and enantioselective single-site solid catalysts for C-C bond formation reactions. Treatment of E-MOF with [RhCl(CH)] led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to α,β-unsaturated ketones, whereas treatment of E-MOF with Rh(acac)(CH) afforded a highly efficient catalyst for the asymmetric 1,2-additions of arylboronic acids to aldimines. Interestingly, E-MOF·Rh(acac) showed higher activity and enantioselectivity than the homogeneous control catalyst, likely due to the formation of a true single-site catalyst in the MOF. E-MOF·Rh(acac) was also successfully recycled and reused at least seven times without loss of yield and enantioselectivity.