Dirhodium(II)/Phosphine Catalyst with Chiral Environment at Bridging Site and Its Application in Enantioselective Atropisomer Synthesis.

ABSTRACT: A dirhodium(II)/phosphine catalyst with a chiral environment at the bridging site was developed for the asymmetric arylation of phenanthrene-9,10-diones with arylboronic acids. In contrast to the classic chiral bridging carboxylic acid (or derivatives) ligand strategy of bimetallic dirhodium(II) catalysis, in this reaction, tuning both axial and bridging ligands realized the first Rh₂(OAc)₄/phosphine-catalyzed highly enantioselective carbonyl addition reaction. The kinetic analysis reveals that dirhodium(II) and arylboronic acid follow the first-order kinetics, while phenanthrene-9,10-dione is zeroth-order. These data supported the proposed catalytic cycle, where the key intermediate in the rate-determining step involved the dirhodium(II) complex and arylboronic acid.

SUBMITTER: Shi L 

PROVIDER: S-EPMC10141619 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature