title: Rh(I)-catalyzed intermolecular hydroacylation: enantioselective cross-coupling of aldehydes and ketoamides.
abstract: Under Rh(I) catalysis, α-ketoamides undergo intermolecular hydroacylation with aliphatic aldehydes. A newly designed Josiphos ligand enables access to α-acyloxyamides with high atom-economy and enantioselectivity. On the basis of mechanistic and kinetic studies, we propose a pathway in which rhodium plays a dual role in activating the aldehyde for cross-coupling. A stereochemical model is provided to rationalize the sense of enantioinduction observed.
authors.affiliation: Department of Chemistry, University of California , Irvine, California 92697, United States.
authors.forename: Kevin G M
authors.initials: KG
authors.lastname: Kou
authors.forename: Diane N
authors.initials: DN
authors.lastname: Le
authors.forename: Vy M
authors.initials: VM
authors.lastname: Dong
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000577:Amides / Q000737:chemistry*; D002384:Catalysis; D060326:Chemistry Techniques, Synthetic; D007553:Isotope Labeling; D007659:Ketones / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D000577:Amides; D007659:Ketones; C520957:beta-ketoamide; D012238:Rhodium; C421487:3-phenylpropanal