Takahiro Sawano, Pengfei Ji, Alexandra R. McIsaac, Zekai Lin, Carter W. Abney Wenbin Lin*
We have designed the first chiral diene-based metal–organic framework (MOF), E2-MOF, and postsynthetically metalated E2-MOF with Rh(I) complexes to afford highly active and enantioselective single-site solid catalysts for C–C bond formation reactions. Treatment of E2-MOF with [RhCl(C2H4)2]2 led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to α,β-unsaturated ketones, whereas treatment of E2-MOF with Rh(acac)(C2H4)2 afforded a highly efficient catalyst for the asymmetric 1,2-additions of arylboronic acids to aldimines. Interestingly, E2-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.