State Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education and Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry, Peking University, Beijing 100871, China.
Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, China.
J Org Chem. 2021 Feb 5;86(3):2135-2157. doi: 10.1021/acs.joc.0c02494. Epub 2021 Jan 12.
A concise and diastereoselective construction of the ABCD ring system of spirochensilide A is described. The key steps of this synthesis are a semipinacol rearrangement reaction to stereoselectively construct the AB ring system bearing two vicinal quaternary chiral centers and a Co-mediated Pauson-Khand reaction to form the spiro-based bicyclic CD ring system. This chemistry leads to the stereoselective synthesis of 13()-demethyl spirochensilide A, paving the way for the first asymmetric total synthesis of (-)-spirochensilide A.
本文描述了螺色烯硅素 A 的 ABCD 环系的简洁和非对映选择性构建。该合成的关键步骤包括半频哪醇重排反应，以立体选择性地构建带有两个相邻的季碳手性中心的 AB 环系，以及 Co 介导的 Pauson-Khand 反应，以形成基于螺的双环 CD 环系。这种化学方法导致了 13()-去甲基螺色烯硅素 A 的立体选择性合成，为 (-)-螺色烯硅素 A 的首次不对称全合成铺平了道路。
