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Rh(I)-catalyzed intermolecular hydroacylation: enantioselective cross-coupling of aldehydes and ketoamides.

ABSTRACT: Under Rh(I) catalysis, ?-ketoamides undergo intermolecular hydroacylation with aliphatic aldehydes. A newly designed Josiphos ligand enables access to ?-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.

SUBMITTER: Kou KG

PROVIDER: S-EPMC4091274 | biostudies-literature | 2014 Jul

REPOSITORIES: biostudies-literature

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Rh(I)-catalyzed intermolecular hydroacylation: enantioselective cross-coupling of aldehydes and ketoamides.

Kou Kevin G M KG Le Diane N DN Le Diane N DN Dong Vy M VM

Journal of the American Chemical Society 20140617 26

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. ...[more]

PMID: 24937681

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