title: Computationally designed and experimentally confirmed diastereoselective rhodium-catalyzed Pauson-Khand reaction at room temperature.
abstract: The computational analysis of the rhodium-catalyzed Pauson-Khand reaction indicates that the key transition state is highly charge-polarized, wherein different diastereoisomers have distinctively different charge polarization patterns. Experimental studies demonstrate that chloro-enynes provide the optimal σ-electron-withdrawing group to promote polarization and thereby reduce the activation barrier to provide a highly diastereoselective reaction at room temperature.
authors.affiliation: Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, USA. mbaik@indiana.edu
authors.forename: Mu-Hyun
authors.initials: MH
authors.lastname: Baik
authors.forename: Shivnath
authors.initials: S
authors.lastname: Mazumder
authors.forename: Paolo
authors.initials: P
authors.lastname: Ricci
authors.forename: James R
authors.initials: JR
authors.lastname: Sawyer
authors.forename: Ye-Geun
authors.initials: YG
authors.lastname: Song
authors.forename: Huijun
authors.initials: H
authors.lastname: Wang
authors.forename: P Andrew
authors.initials: PA
authors.lastname: Evans
mesh_terms: D002384:Catalysis; D008958:Models, Molecular; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D013696:Temperature
chemical_list: D012238:Rhodium