Guangdong Province Key Laboratory of Pharmacodynamic Constituents of TCM and New Drugs Research, College of Pharmacy, Jinan University, Guangzhou 510632, China.
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
J Am Chem Soc. 2020 Jul 22;142(29):12602-12607. doi: 10.1021/jacs.0c05479. Epub 2020 Jul 13.
The first and asymmetric total synthesis of bioactive bufospirostenin A, an unusual spirostanol with rearranged A/B rings, was accomplished. The synthetically challenging [5-7-6-5] tetracyclic ring system, found in bufospirostenin A and some other natural products, was efficiently constructed by the unique intramolecular rhodium-catalyzed Pauson-Khand reaction of an alkoxyallene-yne. The 11 stereocenters in the final product, including the 10 contiguous stereocenters, were installed diastereoselectively.
生物活性 bufospirostenin A（一种具有重排 A/B 环的罕见螺甾烷醇）的首次不对称全合成已完成。在 bufospirostenin A 和其他一些天然产物中发现的具有合成挑战性的[5-7-6-5]四环体系，通过烷氧基丙二炔的独特的铑催化 Pauson-Khand 反应高效构建。最终产物中的 11 个立体中心，包括 10 个连续的立体中心，都以非对映选择性方式安装。
