Wang Yu, Ju Wei, Tian Hailong, Tian Weisheng, Gui Jinghan
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis , Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences , 345 Lingling Road , Shanghai 200032 , China.
J Am Chem Soc. 2018 Aug 1;140(30):9413-9416. doi: 10.1021/jacs.8b06444. Epub 2018 Jul 19.
A 10-step synthesis of the C25 steroid natural product cyclocitrinol from inexpensive, commercially available pregnenolone is reported. This synthesis features a biomimetic cascade rearrangement to efficiently construct the challenging bicyclo[4.4.1] A/B ring system, which enabled a gram-scale synthesis of the bicyclo[4.4.1] enone intermediate 18 in only nine steps. This work also provides experimental support for the biosynthetic origin of cyclocitrinol.
报道了一种从廉价的市售孕烯醇酮出发，经10步合成C25甾体天然产物环柠檬醇的方法。该合成方法的特点是通过仿生级联重排高效构建具有挑战性的双环[4.4.1] A/B环系，仅需9步就能实现双环[4.4.1]烯酮中间体18的克级规模合成。这项工作还为环柠檬醇的生物合成起源提供了实验支持。
