Stereoselective Synthesis of Polysubstituted Conjugated Dienes Enabled by Photo-Driven Sequential Sigmatropic Rearrangement

被引：6

作者：

Ji, Xin ^{[1
]}

Shen, Chaoren ^{[1
]}

Ni, Yuhao ^{[1
]}

Si, Zhi-Yao ^{[1
]}

Wang, Yuzhu ^{[1
]}

Zhi, Xinrong ^{[1
]}

Zhao, Yuting ^{[1
]}

Peng, Huiling ^{[1
]}

Liu, Lu ^{[1
,2
]}

机构：

[1] East China Normal Univ, Sch Chem & Mol Engn, 500 Dongchuan Rd, Shanghai 200241, Peoples R China

[2] East China Normal Univ, Shanghai Engn Res Ctr Mol Therapeut & New Drug Dev, 3663 N Zhongshan Rd, Shanghai 200062, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2024年 / 63卷 / 24期

基金：

中国国家自然科学基金;

关键词：

diazo compounds; Wolff rearrangement; sigmatropic rearrangement; 1,6-dipolar ion; conjugated diene; COREY-CHAYKOVSKY REACTIONS; DIELS-ALDER REACTIONS; C-N BOND; STEREOSPECIFIC SYNTHESIS; CLAISEN REARRANGEMENT; VINYL AZIRIDINES; CYCLOADDITIONS; CARBENE; ACCESS; EFFICIENT;

D O I：

10.1002/anie.202400805

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We here reported a highly stereoselective method for the synthesis of polysubstituted conjugated dienes from alpha-aryl alpha-diazo alkynyl ketones and pyrazole-substituted unsymmetric aminals under mild conditions, which was promoted by photo-irridation and involved with 1,6-dipolar intermediate and quadruple sigmatropic rearrangements, was successfully developed. In this transformation, the cleavage of four bonds and the recombination of five bonds were implemented in one operational step. This protocol provided a modular tool for constructing dienes from amines, pyrazoles and alpha-alkynyl-alpha-diazoketones in one-pot manner. The results of mechanistic investigation indicated that the plausible reaction path underwent the 1,6-sigmatropic rearrangement instead of the 1,5-sigmatropic rearrangement. An unprecedented photo-driven quadruple sequential sigmatropic rearrangements of alpha-aryl alpha-diazo alkynylketones with aminals via 1,6-dipolar ion intermediate is disclosed. This protocol provides a facile access to synthetically useful multi-substituted conjugated dienes in highly stereoselective manner via visible light catalysis in mild conditions.+ image

引用

页数：8

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