Institute of Organic Chemistry, University of Konstanz, Universitätsstrasse 10, Konstanz 78464, Germany.
Institute of Inorganic Chemistry, University of Konstanz, Universitätsstrasse 10, Konstanz 78464, Germany.
J Am Chem Soc. 2021 Aug 11;143(31):11934-11938. doi: 10.1021/jacs.1c05257. Epub 2021 Jul 29.
The first asymmetric synthesis of pepluanol A () is presented. The synthesis route is very concise (10 steps) and features a Curtin-Hammett-driven stereoconvergent intramolecular Diels-Alder reaction. A Nozaki-Hiyama-Kishi reaction comprises the connective step, bringing together the seven-membered enone system bearing the dienophile and the diene in the side chain. Subsequent stereoconvergent IMDA reaction furnishes the carboskeleton of the natural product in only 7 steps. The reactions were carried out on a gram scale up to an advanced intermediate and including the stereoconvergent intramolecular Diels-Alder reaction.
首次实现了 pepluanol A () 的不对称全合成。该合成路线非常简洁（10 步），具有 Curtin-Hammett 驱动的立体协同分子内 Diels-Alder 反应。Nozaki-Hiyama-Kishi 反应是连接步骤，将带有亲二烯体和侧链二烯的七元烯酮系统组合在一起。随后的立体协同内分子 Diels-Alder 反应仅通过 7 步即可构建天然产物的碳骨架。反应可在克级规模上进行，直至得到高级中间体，包括立体协同内分子 Diels-Alder 反应。
