The first chiral diene-based metal–organic frameworks for highly enantioselective carbon–carbon bond formation reactions† †Electronic supplementary information (ESI) available: General experimental section; synthesis and characterization of ligand LH2 and E2-MOF; XAFS experiments and analyses; MOF-catalyzed asymmetric additions of arylboronic acids to α,β-unsaturated ketones and aldimines. CCDC 1064133. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc0210

The first chiral rhodium-diene-based metal–organic frameworks are highly active and enantioselective catalysts for C–C 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.