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Copper-Catalyzed Enantioselective Allylic Alkylation with a ?-Butyrolactone-Derived Silyl Ketene Acetal.

ABSTRACT: Herein, we report a Cu-catalyzed enantioselective allylic alkylation using a ?-butyrolactone-derived silyl ketene acetal. Critical to the development of this work was the identification of a novel mono-picolinamide ligand with the appropriate steric and electronic properties to afford the desired products in high yield (up to 96?%) and high ee (up to 95?%). Aryl, aliphatic, and unsubstituted allylic chlorides bearing a broad range of functionality are well-tolerated. Spectroscopic studies reveal that a Cu^I species is likely the active catalyst, and DFT calculations suggest ligand sterics play an important role in determining Cu coordination and thus catalyst geometry.

SUBMITTER: Jette CI

PROVIDER: S-EPMC7051182 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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Copper-Catalyzed Enantioselective Allylic Alkylation with a γ-Butyrolactone-Derived Silyl Ketene Acetal.

Jette Carina I CI Tong Z Jaron ZJ Hadt Ryan G RG Stoltz Brian M BM

Angewandte Chemie (International ed. in English) 20191216 5

Herein, we report a Cu-catalyzed enantioselective allylic alkylation using a γ-butyrolactone-derived silyl ketene acetal. Critical to the development of this work was the identification of a novel mono-picolinamide ligand with the appropriate steric and electronic properties to afford the desired products in high yield (up to 96 %) and high ee (up to 95 %). Aryl, aliphatic, and unsubstituted allylic chlorides bearing a broad range of functionality are well-tolerated. Spectroscopic studies reveal ...[more]

PMID: 31742854

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