Chiral Ligand‐Decorated Rhodium Nanoparticles Incorporated in Covalent Organic Framework for Asymmetric Catalysis

Abstract While metal nanoparticles (NPs) have demonstrated their great potential in catalysis, introducing chiral microenvironment around metal NPs to achieve efficient conversion and high enantioselectivity remains a long‐standing challenge. In this work, tiny Rh NPs, modified by chiral diene ligands (Lx) bearing diverse functional groups, are incorporated into a covalent organic framework (COF) for the asymmetric 1,4‐addition reactions between arylboronic acids and nitroalkenes. Though Rh NPs hosted in the COF are inactive, decorating Rh NPs with Lx creates the active Rh−Lx interface and induces high activity. Moreover, chiral microenvironment modulation around Rh NPs by altering the groups on chiral diene ligands greatly optimizes the enantioselectivity (up to 95.6 % ee). Mechanistic investigations indicate that the formation of hydrogen‐bonding interaction between Lx and nitroalkenes plays critical roles in the resulting enantioselectivity. This work highlights the significance of chiral microenvironment modulation around metal NPs by chiral ligand decoration for heterogeneous asymmetric catalysis.