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(C2H4)(2)](2) led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to alpha,beta-unsaturated ketones, whereas treatment of E-2-MOF with Rh(acac)(C2H4)(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.E2-MOF.Rh(acac) was also successfully recycled and reused at least seven times without loss of yield and enantioselectivity.