Synthesis of the DEF-Ring Spirocyclic Core of Cyclopamine

被引：2

作者：

Shao, Hao ^{[1
]}

Liu, Wenheng ^{[1
]}

Fang, Zhengqi ^{[1
]}

He, Haibing ^{[1
,2
]}

Gao, Shuanhu ^{[1
,2
]}

机构：

[1] East China Normal Univ, Sch Chem & Mol Engn, Shanghai Key Lab Green Chem & Chem Proc, State Key Lab Petr Mol & Proc Engn, Shanghai 200062, Peoples R China

[2] East China Normal Univ, Wuhu Hosp, Sch Chem & Mol Engn, Shanghai Frontiers Sci Ctr Mol Intelligent Synth, Shanghai 200062, Peoples R China

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2024年 / 89卷 / 06期

基金：

中国国家自然科学基金;

关键词：

VERATRUM ALKALOID SERIES; DIELS-ALDER REACTIONS; HEDGEHOG PATHWAY; VINYLOGOUS MANNICH; ASYMMETRIC-SYNTHESIS; MEDULLOBLASTOMA; DEAROMATIZATION; DERIVATIVES; CONVERGENT; EFFICIENT;

D O I：

10.1021/acs.joc.3c02804

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A stereoselective synthesis of the DEF-ring spirocyclic core of cyclopamine was accomplished using commercially available materials. The key steps in the synthesis were (i) the enantioselective vinylogous Mannich reaction, followed by lactamization to generate the piperidine F ring, and (ii) intramolecular oxidative dearomative spiroetherification to construct the DEF-ring spirocyclic core of cyclopamine. We found that the stereochemistry of the spirocyclization was controlled by the configuration of the methyl group (C-20) in the substrate.

引用

页码：4215 / 4220

页数：6

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