Calcium carbide as the acetylide source: transition-metal-free synthesis of substituted pyrazoles via [1,5]-sigmatropic rearrangements

被引：68

作者：

Yu, Yue ^{[1
]}

Huang, Wei ^{[1
]}

Chen, Yang ^{[1
]}

Gao, Bingjie ^{[1
]}

Wu, Wanqing ^{[1
]}

Jiang, Huanfeng ^{[1
]}

机构：

[1] South China Univ Technol, Sch Chem & Chem Engn, Key Lab Funct Mol Engn Guangdong Prov, Guangzhou 510640, Guangdong, Peoples R China

来源：

GREEN CHEMISTRY | 2016年 / 18卷 / 24期

基金：

中国国家自然科学基金;

关键词：

ONE-POT SYNTHESIS; N BOND-FORMATION; ORGANIC-SYNTHESIS; 3,5-DISUBSTITUTED PYRAZOLES; SIGMATROPIC REARRANGEMENT; TETRANYCHUS-URTICAE; CARBONYL-COMPOUNDS; TOSYLHYDRAZONES; KETONES; CASCADE;

D O I：

10.1039/c6gc02776h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Under transition-metal-free conditions, calcium carbide was used as the acetylide source to react with a wide range of N-tosylhydrazones derived from aldehydes or ketones, affording various substituted pyrazoles in good yields with high regio-selectivities. The transformations go through [3 + 2] cycloadditions followed by [1,5]-sigmatropic rearrangements, which are supported by deuterium-labeling experiments.

引用

页码：6445 / 6449

页数：5

共 62 条

[1]

Barluenga J., 2011, ANGEW CHEM INT EDIT, V50, P7486

[2] Reductive Azidation of Carbonyl Compounds via Tosylhydrazone Intermediates Using Sodium Azide [J].

Barluenga, Jose ;

Tomas-Gamasa, Maria ;

Valdes, Carlos .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (24) :5950-5952

[3] Straightforward Synthesis of Ethers: Metal-Free Reductive Coupling of Tosylhydrazones with Alcohols or Phenols [J].

Barluenga, Jose ;

Tomas-Gamasa, Maria ;

Aznar, Fernando ;

Valdes, Carlos .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (29) :4993-4996

[4] Regioselective One-Step Synthesis of Pyrazoles from Alkynes and N-Tosylhydrazones: [3+2] Dipolar Cycloaddition/[1,5] Sigmatropic Rearrangement Cascade [J].

Carmen Perez-Aguilar, M. ;

Valdes, Carlos .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (28) :7219-7223

[5] Organic Synthesis "On Water" [J].

Chanda, Arani ;

Fokin, Valery V. .

CHEMICAL REVIEWS, 2009, 109 (02) :725-748

[6] Calcium carbide as a cost-effective starting material for symmetrical diarylethynes via Pd-catalyzed coupling reaction [J].

Chuentragool, Padon ;

Vongnam, Kunnigar ;

Rashatasakhon, Paitoon ;

Sukwattanasinitt, Mongkol ;

Wacharasindhu, Sumrit .

TETRAHEDRON, 2011, 67 (42) :8177-8182

[7] The chemical development of the commercial route to sildenafil: A case history [J].

Dale, DJ ;

Dunn, PJ ;

Golightly, C ;

Hughes, ML ;

Levett, PC ;

Pearce, AK ;

Searle, PM ;

Ward, G ;

Wood, AS .

ORGANIC PROCESS RESEARCH & DEVELOPMENT, 2000, 4 (01) :17-22

[8] Base-mediated reaction of hydrazones and nitroolefins with a reversed regio selectivity: A novel synthesis of 1,3,4-trisubstituted pyrazoles [J].

Deng, Xiaohu ;

Mani, Neelakandha S. .

ORGANIC LETTERS, 2008, 10 (06) :1307-1310

[9] Synthesis of thioethers via metal-free reductive coupling of tosylhydrazones with thiols [J].

Ding, Qiuping ;

Cao, Banpeng ;

Yuan, Jianjun ;

Liu, Xianjin ;

Peng, Yiyuan .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2011, 9 (03) :748-751

[10] Visible-Light Photocatalytic Aerobic Annulation for the Green Synthesis of Pyrazoles [J].

Ding, Ya ;

Zhang, Te ;

Chen, Qiu-Yun ;

Zhu, Chunyin .

ORGANIC LETTERS, 2016, 18 (17) :4206-4209

← 1 2 3 4 5 6 7 →