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Convergent Total Synthesis of Principinol D, a Rearranged Kaurane Diterpenoid.

ABSTRACT: The total synthesis of principinol D, a rearranged kaurane diterpenoid, is reported. This grayanane natural product is constructed via a convergent fragment coupling approach, wherein the central seven-membered ring is synthesized at a late stage. The bicyclo[3.2.1]octane fragment is accessed by a Ni-catalyzed ?-vinylation reaction. Strategic reductions include a diastereoselective SmI2-mediated ketone reduction with PhSH and a new protocol for selective ester reduction in the presence of ketones. The convergent strategy reported herein may be an entry point to the larger class of kaurane diterpenoids.

SUBMITTER: Turlik A

PROVIDER: S-EPMC7192013 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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Convergent Total Synthesis of Principinol D, a Rearranged Kaurane Diterpenoid.

Turlik Aneta A Chen Yifeng Y Scruse Anthony C AC Newhouse Timothy R TR

Journal of the American Chemical Society 20190507 20

The total synthesis of principinol D, a rearranged kaurane diterpenoid, is reported. This grayanane natural product is constructed via a convergent fragment coupling approach, wherein the central seven-membered ring is synthesized at a late stage. The bicyclo[3.2.1]octane fragment is accessed by a Ni-catalyzed α-vinylation reaction. Strategic reductions include a diastereoselective SmI<sub>2</sub>-mediated ketone reduction with PhSH and a new protocol for selective ester reduction in the presenc ...[more]

PMID: 31042866

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