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Enantio-, diastereo-, and regioselective iridium-catalyzed asymmetric allylic alkylation of acyclic ?-ketoesters.

ABSTRACT: The first regio-, diastereo-, and enantioselective allylic alkylation of acyclic ?-ketoesters to form vicinal tertiary and all-carbon quaternary stereocenters is reported. Critical to the successful development of this method was the employment of iridium catalysis in concert with N-aryl-phosphoramidite ligands. Broad functional group tolerance is observed at the keto-, ester-, and ?-positions of the nucleophile. Various transformations demonstrating the utility of this method for rapidly accessing complex enantioenriched compounds are reported.

SUBMITTER: Liu WB

PROVIDER: S-EPMC3881553 | biostudies-literature | 2013 Nov

REPOSITORIES: biostudies-literature

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Enantio-, diastereo-, and regioselective iridium-catalyzed asymmetric allylic alkylation of acyclic β-ketoesters.

Liu Wen-Bo WB Reeves Corey M CM Stoltz Brian M BM

Journal of the American Chemical Society 20131106 46

The first regio-, diastereo-, and enantioselective allylic alkylation of acyclic β-ketoesters to form vicinal tertiary and all-carbon quaternary stereocenters is reported. Critical to the successful development of this method was the employment of iridium catalysis in concert with N-aryl-phosphoramidite ligands. Broad functional group tolerance is observed at the keto-, ester-, and α-positions of the nucleophile. Various transformations demonstrating the utility of this method for rapidly access ...[more]

PMID: 24160327

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