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Enantioselective Total Synthesis of (+)-Peniciketals A and B: Two Architecturally Complex Spiroketals.

ABSTRACT: The enantioselective total syntheses of (+)-peniciketals A and B, two members of a family of architecturally complex spiroketals, have been achieved. Key synthetic transformations comprise Type I Anion Relay Chemistry (ARC) to construct the benzannulated [6,6]-spiroketal skeleton, a Negishi cross-coupling/olefin cross-metathesis reaction sequence to generate the trans-enone structure, and a late-stage large fragment union exploiting our recently developed photoisomerization/cyclization tactic.

SUBMITTER: Deng Y

PROVIDER: S-EPMC8170783 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Enantioselective Total Synthesis of (+)-Peniciketals A and B: Two Architecturally Complex Spiroketals.

Deng Yifan Y Yang Chia-Ping H CH Smith Iii Amos B AB

Journal of the American Chemical Society 20210126 4

The enantioselective total syntheses of (+)-peniciketals A and B, two members of a family of architecturally complex spiroketals, have been achieved. Key synthetic transformations comprise Type I Anion Relay Chemistry (ARC) to construct the benzannulated [6,6]-spiroketal skeleton, a Negishi cross-coupling/olefin cross-metathesis reaction sequence to generate the <i>trans</i>-enone structure, and a late-stage large fragment union exploiting our recently developed photoisomerization/cyclization ta ...[more]

PMID: 33496178

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