Total Synthesis of Stemarene and Betaerene Diterpenoids: Divergent Ring-Formation Strategy and Late-Stage C-H Functionalization (vol 4, pg 987, 2022)

被引：10

作者：

Chen, Renzhi

机构：

[1] Department of Chemistry, Department of Chemical Biology, Key Laboratory of Chemical Biology of Fujian Province, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian

来源：

CCS CHEMISTRY | 2022年 / 4卷 / 03期

基金：

中国国家自然科学基金;

关键词：

diterpenoids; divergent synthesis; late-stage C-H functionalization; structure reassignment; total synthesis;

D O I：

10.31635/ccschem.021.202100821

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A unified protecting group-free approach to two stemarene and two betaerene diterpenoids through a bioinspired two-phase strategy has been developed, and three of them were obtained for the first time via chemical synthesis. Starting from a common intermediate, two distinct tetracyclic frameworks containing diastereoisomeric bridged bicycles were constructed by a divergent ring reorganization strategy. Late-stage C-H functionalization through a xanthylation-oxygenation protocol furnished the corresponding oxygenated stereocenters or oxo functionality in high regio- and diastereoselective fashion within a complex hydrocarbon system. The stereochemical puzzles in (-)-2-acetoxybetaer- 13(17)-ene and (+)-7-acetoxybetaer-13(17)-ene were first predicted by the comparison of density functional theory (DFT)-nuclear magnetic resonance (NMR) data with the reported data and then unambiguously addressed through the total syntheses of natural products and three diastereomers. © 2022 Chinese Chemical Society. All right reserved.

引用

页码：1109 / 1109

页数：1