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

作者：Yifan Deng, Chia‐Ping Huang Yang, Amos B. Smith · 发表于：Journal of the American Chemical Society · 年份：2021 · DOI：10.1021/jacs.0c11424 · 被引用次数：17 · 研究领域：Synthetic Organic Chemistry Methods、Marine Toxins and Detection Methods、Marine Sponges and Natural Products

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.