State Key Laboratory of Chemical Oncogenomics and Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, 518055, China.
Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Beijing National Laboratory for Molecular Science and Peking-Tsinghua Center for Life Sciences, Peking University, Beijing, 100871, China.
J Am Chem Soc. 2021 Nov 3;143(43):18287-18293. doi: 10.1021/jacs.1c08880. Epub 2021 Oct 20.
A convenient enantioselective total synthesis of (+)-cyclobutastellettolide B via a strategy that involves a diastereoselective Johnson-Claisen rearrangement, a regioselective cyclopropoxytrimethylsilane ring-opening reaction, and a Norrish-Yang cyclization is described. The results of computational and experimental studies indicate that the regio- and stereoselectivity of the Norrish-Yang reaction are controlled by the C-H bond dissociation energy and restricted rotation of the C13-C14 bond.
通过采用包含立体选择性 Johnson-Claisen 重排、区域选择性环丙氧基三甲基硅烷开环反应和 Norrish-Yang 环化反应的策略，实现了（+）-环巴托石蒜内酯 B 的一种方便的对映选择性全合成。计算和实验研究结果表明，Norrish-Yang 反应的区域和立体选择性受 C-H 键离解能和 C13-C14 键限制旋转的控制。
