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Total Synthesis of (-)-Xylogranatopyridine B via a Palladium-Catalyzed Oxidative Stannylation of Enones.

ABSTRACT: We report a total synthesis of the pyridine-containing limonoid alkaloid (-)-xylogranatopyridine B in 11 steps from commercially available dihydrocarvone. The central pyridine ring was assembled by a late-stage fragment coupling approach employing a modified Liebeskind pyridine synthesis. One fragment was prepared by an allyl-palladium catalyzed oxidative enone ?-stannylation, in which the key bimetallic ?-stannyl palladium enolate intermediate undergoes a ?-hydride elimination. This methodology also allowed introduction of alkyl and silyl groups to the ?-position of enones.

SUBMITTER: Schuppe AW

PROVIDER: S-EPMC6499388 | biostudies-literature | 2018 Feb

REPOSITORIES: biostudies-literature

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Total Synthesis of (-)-Xylogranatopyridine B via a Palladium-Catalyzed Oxidative Stannylation of Enones.

Schuppe Alexander W AW Huang David D Chen Yifeng Y Newhouse Timothy R TR

Journal of the American Chemical Society 20180205 6

We report a total synthesis of the pyridine-containing limonoid alkaloid (-)-xylogranatopyridine B in 11 steps from commercially available dihydrocarvone. The central pyridine ring was assembled by a late-stage fragment coupling approach employing a modified Liebeskind pyridine synthesis. One fragment was prepared by an allyl-palladium catalyzed oxidative enone β-stannylation, in which the key bimetallic β-stannyl palladium enolate intermediate undergoes a β-hydride elimination. This methodology ...[more]

PMID: 29338207

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