Enantioselective Total Synthesis of (-)-Rubriflordilactone B by a Bioinspired Skeletal Reorganization Approach

被引：2

作者：

Xie, Yancheng ^{[1
]}

Bao, Jiajing ^{[1
]}

Wang, Yu ^{[1
]}

Shen, Yi ^{[1
]}

Liang, Zexuan ^{[1
]}

Tian, Hailong ^{[1
]}

Gui, Jinghan ^{[1
]}

机构：

[1] Univ Chinese Acad Sci, Shanghai Inst Organ Chem, Chinese Acad Sci, State Key Lab Chem Biol, Shanghai 200032, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2025年 / 147卷 / 09期

基金：

中国国家自然科学基金;

关键词：

ASYMMETRIC TOTAL-SYNTHESIS; DEFG-RING-SYSTEM; STEREOSELECTIVE-SYNTHESIS; RUBRIFLORDILACTONE-B; CONJUGATED DIENONES; EFFICIENT SYNTHESIS; REARRANGEMENT; KETONES; TRITERPENOIDS; CONSTRUCTION;

D O I：

10.1021/jacs.4c18292

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Rubriflordilactone B is a Schisandra bisnortriterpenoid with a unique 5/5/7/6/5/5-hexacyclic framework that includes a characteristic tetrasubstituted aromatic ring. Herein, we report a convergent, enantioselective total synthesis of this natural product by a bioinspired skeletal reorganization approach. Key transformations include a chelation-controlled [2,3]-Wittig-Still rearrangement to assemble the western cyclohexenyl fragment with complete diastereocontrol, a Cu(II)-catalyzed tandem acyloin acylation-Wittig olefin to build the eastern butanolide fragment, a Friedel-Crafts cyclization to construct the seven-membered ring, and an E1cB reaction/transesterification/oxa-Michael addition cascade to forge the pivotal 5/5-fused bicyclic lactone. This work vividly demonstrates that bioinspired skeletal reorganization is a useful strategy for simplifying the retrosynthetic analysis of structurally complex natural products.

引用

页码：7875 / 7885

页数：11

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