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Iridium-catalyzed enantioselective allylic substitution of unstabilized enolates derived from ?,?-unsaturated ketones.

ABSTRACT: We report Ir-catalyzed, enantioselective allylic substitution reactions of unstabilized silyl enolates derived from ?,?-unsaturated ketones. Asymmetric allylic substitution of a variety of allylic carbonates with silyl enolates gave allylated products in 62-94% yield with 90-98% ee and >20:1 branched-to-linear selectivity. The synthetic utility of this method was illustrated by the short synthesis of an anticancer agent, TEI-9826.

SUBMITTER: Chen M

PROVIDER: S-EPMC4159307 | biostudies-literature | 2014 Aug

REPOSITORIES: biostudies-literature

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Iridium-catalyzed enantioselective allylic substitution of unstabilized enolates derived from α,β-unsaturated ketones.

Chen Ming M Hartwig John F JF

Angewandte Chemie (International ed. in English) 20140610 33

We report Ir-catalyzed, enantioselective allylic substitution reactions of unstabilized silyl enolates derived from α,β-unsaturated ketones. Asymmetric allylic substitution of a variety of allylic carbonates with silyl enolates gave allylated products in 62-94% yield with 90-98% ee and >20:1 branched-to-linear selectivity. The synthetic utility of this method was illustrated by the short synthesis of an anticancer agent, TEI-9826. ...[more]

PMID: 24917569

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