Visible-light-induced [3+2] cycloadditions of donor/donor diazo intermediates with alkenes to achieve (spiro)-pyrazolines and pyrazoles

被引：26

作者：

Zhang, Yu ^{[1
]}

Li, Yanchuan ^{[2
,3
]}

Ni, Shao-Fei ^{[4
]}

Li, Jin-Peng ^{[4
]}

Xia, Dingding ^{[1
]}

Han, Xinyu ^{[1
,3
]}

Lin, Jingchuan ^{[1
,3
]}

Wang, Jinxin ^{[3
]}

Das, Shoubhik ^{[3
,5
,6
]}

Zhang, Wei-Dong ^{[1
,2
,3
,7
]}

机构：

[1] Shanghai Univ Tradit Chinese Med, Inst Interdisciplinary Integrat Med Res, Shanghai Frontiers Sci Ctr Chinese Med Chem Biol, 1200 Cailun Rd, Shanghai 201203, Peoples R China

[2] Zhejiang Chinese Med Univ, Sch Pharmaceut Sci, Hangzhou 310053, Peoples R China

[3] Second Mil Med Univ, Sch Pharm, Shanghai 200433, Peoples R China

[4] Shantou Univ, Key Lab Preparat & Applicat Ordered Struct Mat Gu, Dept Chem, Shantou 515063, Peoples R China

[5] Univ Antwerp, Dept Chem, Antwerp, Belgium

[6] Univ Bayreuth, Dept Chem, Bayreuth, Germany

[7] Chinese Acad Med Sci & Peking Union Med Coll, GInstitute Med Plant Dev, Beijing 100193, Peoples R China

来源：

CHEMICAL SCIENCE | 2023年 / 14卷 / 38期

基金：

中国国家自然科学基金;

关键词：

N-TOSYLHYDRAZONES; 1,3-DIPOLAR CYCLOADDITION; ARYNES;

D O I：

10.1039/d3sc04188c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

To date, [3 + 2] cycloadditions of diazo esters with alkynes or alkenes have been a robust tool to generate pyrazoles and pyrazolines. However, methods capable of generating donor/donor diazo species from readily available N-tosylhydrazones to furnish [3 + 2] cycloadditions, remain elusive. Herein, we describe the first visible-light-induced [3 + 2] cycloadditions of donor/donor diazo precursors with alkenes to afford pyrazoles and novel (spiro)pyrazolines bearing a quaternary center. This protocol shows a tolerable substrate scope covering versatile carbonyl compounds and alkenes. Late-stage functionalization of bioactive molecules, one-pot approach, and gram-scale synthesis have also been introduced successfully to prove the practicability. At last, mechanistic experiments and DFT studies suggested the formation of non-covalent interactions enabling the activation of N-tosylhydrazones and the formation of the donor/donor diazo intermediates. Visible-light-induced [3+2] cycloadditions of donor/donor diazo precursors with alkenes to afford pyrazoles and (spiro)pyrazolines have been reported. Mechanistic and DFT studies suggested the non-covalent interactions promote the reaction.

引用

页码：10411 / 10419

页数：10

共 61 条

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