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(2)-MOF, and postsynthetically metalated E(2)-MOF with Rh(i) complexes to afford highly active and enantioselective single-site solid catalysts for C–C bond formation reactions. Treatment of E(2)-MOF with [RhCl(C(2)H(4))(2)](2) led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to α,β-unsaturated ketones, whereas treatment of E(2)-MOF with Rh(acac)(C(2)H(4))(2) afforded a highly efficient catalyst for the asymmetric 1,2-additions of arylboronic acids to aldimines. Interestingly, E(2)-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(2)-MOF·Rh(acac) was also successfully recycled and reused at least seven times without loss of yield and enantioselectivity.