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Catalytic Asymmetric Total Synthesis of (-)-Actinophyllic Acid.

ABSTRACT: Described herein is a catalytic asymmetric total synthesis of (-)-actinophyllic acid, with the key step being a chiral phosphine-catalyzed [3 + 2] annulation between an imine and an allenoate to form a pyrroline intermediate in 99% yield and 94% ee. The synthesis also features CuI-catalyzed coupling between a ketoester and a 2-iodoindole to shape the tetrahydroazocine ring; intramolecular alkylative lactonization; SmI2-mediated intramolecular pinacol coupling between ketone and lactone subunits to assemble the complex skeleton of (-)-actinophyllic acid; and an unprecedented regioselective dehydroxylation.

SUBMITTER: Cai L

PROVIDER: S-EPMC4920546 | biostudies-literature | 2016 Mar

REPOSITORIES: biostudies-literature

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Catalytic Asymmetric Total Synthesis of (-)-Actinophyllic Acid.

Cai Lingchao L Zhang Kui K Kwon Ohyun O

Journal of the American Chemical Society 20160304 10

Described herein is a catalytic asymmetric total synthesis of (-)-actinophyllic acid, with the key step being a chiral phosphine-catalyzed [3 + 2] annulation between an imine and an allenoate to form a pyrroline intermediate in 99% yield and 94% ee. The synthesis also features CuI-catalyzed coupling between a ketoester and a 2-iodoindole to shape the tetrahydroazocine ring; intramolecular alkylative lactonization; SmI2-mediated intramolecular pinacol coupling between ketone and lactone subunits ...[more]

PMID: 26910382

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