Graduate School of Pharmaceutical Sciences, Nagoya City University, 3-1 Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan.
Molecules. 2020 Apr 1;25(7):1610. doi: 10.3390/molecules25071610.
Total syntheses of the labdane diterpene lactones marrubiin, marrulibacetal, desertine, marrulibacetal A, marrubasch F, cyllenine C, marrulanic acid, and marrulactone are described. The -decalin moiety of these molecules was constructed in a stereoselective manner by a Pauson-Khand reaction, and the resultant cyclopentenone was oxidatively cleaved for formation of the lactone ring. Elongation of the side chain at C9 was achieved by an epoxide-opening reaction with a variety of nucleophiles, and the functional group manipulations completed the syntheses of these natural products. Stereochemistries of desertine could be established by the transformations.
本文描述了拉巴烷二萜内酯马鲁宾、马鲁利巴缩醛、沙漠宁、马鲁利巴缩醛 A、马鲁巴什 F、西伦宁 C、马鲁拉烷酸和马鲁内酯的全合成。这些分子的 - 去甲部分通过 Pauson-Khand 反应以立体选择性方式构建，所得环戊烯酮经氧化裂解形成内酯环。C9 位侧链的延长通过与各种亲核试剂的环氧化物开环反应实现，官能团操作完成了这些天然产物的合成。通过转化可以确定沙漠宁的立体化学。
