N-Heterocyclic Carbene-Mediated Microfluidic Oxidative Electrosynthesis of Amides from Aldehydes

被引：76

作者：

Green, Robert A. ^{[1
]}

Pletcher, Derek ^{[1
]}

Leach, Stuart G. ^{[2
]}

Brown, Richard C. D. ^{[1
]}

机构：

[1] Univ Southampton, Dept Chem, Southampton SO17 1BJ, Hants, England

[2] GlaxoSmithKline, Stevenage SG1 2NY, Herts, England

来源：

ORGANIC LETTERS | 2016年 / 18卷 / 05期

基金：

英国工程与自然科学研究理事会;

关键词：

ORGANOCATALYZED ANODIC-OXIDATION; COUPLING REAGENTS; CARBOXYLIC-ACIDS; BOND FORMATION; CATALYSIS; AMIDATION; ESTERS; AMINES; ALCOHOLS; CELL;

D O I：

10.1021/acs.orglett.6b00339

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A flow process for N-Heterocyclic Carbene (NHC)-mediated anodic oxidative amidation of aldehydes is described, employing an undivided microfluidic electrolysis cell to oxidize Breslow intermediates. After electrochemical oxidation, the reaction of the intermediate N-acylated thiazolium cation with primary amines is completed by passage through a heating cell to achieve high conversion in a single pass. The flow mixing regimen circumvented the issue of competing imine formation between the aldehyde and amine substrates, which otherwise prevented formation of the desired product. High yields (71-99%), productivities (up to 2.6 g h(-1)),and current efficiencies (65-91%) were realized for 19 amides.

引用

页码：1198 / 1201

页数：4

共 29 条

[1] N-Heterocyclic Carbene-Catalyzed Oxidative Amidation of Aldehydes with Amines [J].

Alanthadka, Anitha ;

Maheswari, C. Uma .

ADVANCED SYNTHESIS & CATALYSIS, 2015, 357 (06) :1199-1203

[2] N-heterocyclic carbene-catalyzed redox amidations of α-functionalized aldehydes with amines [J].

Bode, Jeffrey W. ;

Sohn, Stephanie S. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (45) :13798-+

[3] Oxidative amide synthesis directly from alcohols with amines [J].

Chen, Cheng ;

Hong, Soon Hyeok .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2011, 9 (01) :20-26

[4] Key green chemistry research areas - a perspective from pharmaceutical manufacturers [J].

Constable, David J. C. ;

Dunn, Peter J. ;

Hayler, John D. ;

Humphrey, Guy R. ;

Leazer, Johnnie L., Jr. ;

Linderman, Russell J. ;

Lorenz, Kurt ;

Manley, Julie ;

Pearlman, Bruce A. ;

Wells, Andrew ;

Zaks, Aleksey ;

Zhang, Tony Y. .

GREEN CHEMISTRY, 2007, 9 (05) :411-420

[5] Catalysis with N-Heterocyclic Carbenes under Oxidative Conditions [J].

De Sarkar, Suman ;

Biswas, Anup ;

Samanta, Ramesh C. ;

Studer, Armido .

CHEMISTRY-A EUROPEAN JOURNAL, 2013, 19 (15) :4664-4678

[6] Oxidative Amidation and Azidation of Aldehydes by NHC Catalysis [J].

De Sarkar, Suman ;

Studer, Armido .

ORGANIC LETTERS, 2010, 12 (09) :1992-1995

[7] N-Heterocyclic Carbene Catalyzed Enantioselective α-Fluorination of Aliphatic Aldehydes and α-Chloro Aldehydes: Synthesis of α-Fluoro Esters, Amides, and Thioesters [J].

Dong, Xiuqin ;

Yang, Wen ;

Hu, Weimin ;

Sun, Jianwei .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (02) :660-663

[8] Peptide Coupling Reagents, More than a Letter Soup [J].

El-Faham, Ayman ;

Albericio, Fernando .

CHEMICAL REVIEWS, 2011, 111 (11) :6557-6602

[9] Internal redox amidation of α,β-unsaturated aldehydes in ionic liquids. The electrochemical route [J].

Feroci, Marta ;

Chiarotto, Isabella ;

Inesi, Achille .

ELECTROCHIMICA ACTA, 2013, 89 :692-699

[10] Organocatalyzed Anodic Oxidation of Aldehydes [J].

Finney, Eric E. ;

Ogawa, Kelli A. ;

Boydston, Andrew J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (30) :12374-12377

← 1 2 3 →