Well-Defined Phosphine-Free Iron-Catalyzed N-Ethylation and N-Methylation of Amines with Ethanol and Methanol

被引：118

作者：

Lator, Alexis ^{[1
]}

Gaillard, Sylvain ^{[1
]}

Poater, Albert ^{[2
]}

Renaud, Jean-Luc ^{[1
]}

机构：

[1] Normandie Univ, LCMT, ENSICAEN, UNICAEN,CNRS, 6 Blvd Marechal Juin, F-14000 Caen, France

[2] Univ Girona, Dept Quim, IQCC, C Ma Aurelia Capmany 69, Girona 17003, Catalonia, Spain

来源：

ORGANIC LETTERS | 2018年 / 20卷 / 19期

关键词：

LIGAND-EXCHANGE REACTION; TRICARBONYL COMPLEXES; REDUCTIVE METHYLATION; AROMATIC-AMINES; CARBON-DIOXIDE; FORMIC-ACID; ALKYLATION; EFFICIENT; NITRILES; ALCOHOLS;

D O I：

10.1021/acs.orglett.8b02080

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An iron(0) complex bearing a cyclopentadienone ligand catalyzed N-methylation and N-ethylation of aryl and aliphatic amines with methanol or ethanol in mild and basic conditions through a hydrogen autotransfer borrowing process is reported. A broad range of aromatic and aliphatic amines underwent mono- or dimethylation in high yields. DFT calculations suggest molecular hydrogen acts not only as a reducing agent but also as an additive to displace thermodynamic equilibria.

引用

页码：5985 / 5990

页数：6

共 60 条

[1] The Catalytic Amination of Alcohols
Baehn, Sebastian
Imm, Sebastian
Neubert, Lorenz
Zhang, Min
Neumann, Helfried
Beller, Matthias
[J]. CHEMCATCHEM, 2011, 3 (12) : 1853 - 1864
[2] Selective Synthesis of Trimethylamine by Catalytic N-Methylation of Ammonia and Ammonium Chloride by utilizing Carbon Dioxide and Molecular Hydrogen
Beydoun, Kassem
Thenert, Katharina
Streng, Emilia S.
Brosinski, Sandra
Leitner, Walter
Klankermayer, Juergen
[J]. CHEMCATCHEM, 2016, 8 (01) : 135 - 138
[3] Ruthenium-Catalyzed Reductive Methylation of Imines Using Carbon Dioxide and Molecular Hydrogen
Beydoun, Kassem
Ghattas, Ghazi
Thenert, Katharina
Klankermayer, Juergen
Leitner, Walter
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (41) : 11010 - 11014
[4] Use of (Cyclopentadienone)iron Tricarbonyl Complexes for C-N Bond Formation Reactions between Amines and Alcohols
Brown, Thomas J.
Cumbes, Madeleine
Diorazio, Louis J.
Clarkson, Guy J.
Wills, Martin
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2017, 82 (19) : 10489 - 10503
[5] Mono-N-methylation of anilines with methanol catalyzed by a manganese pincer-complex
Bruneau-Voisine, Antoine
Wang, Ding
Dorcet, Vincent
Roisnel, Thierry
Darcel, Christophe
Sortais, Jean-Baptiste
[J]. JOURNAL OF CATALYSIS, 2017, 347 : 57 - 62
[6] A general protocol for the reductive N-methylation of amines using dimethyl carbonate and molecular hydrogen: mechanistic insights and kinetic studies
Cabrero-Antonino, Jose R.
Adam, Rosa
Junge, Kathrin
Beller, Matthias
[J]. CATALYSIS SCIENCE & TECHNOLOGY, 2016, 6 (22) : 7956 - 7966
[7] Selective Hydrogenation of Nitriles to Secondary Imines Catalyzed by an Iron Pincer Complex
Chakraborty, Subrata
Milstein, David
[J]. ACS CATALYSIS, 2017, 7 (06): : 3968 - 3972
[8] Selective Monomethylation of Amines with Methanol as the C1 Source
Choi, Geunho
Hong, Soon Hyeok
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2018, 57 (21) : 6166 - 6170
[9] Engineering Metal Organic Frameworks for Heterogeneous Catalysis
Corma, A.
Garcia, H.
Llabres i Xamena, F. X. L. I.
[J]. CHEMICAL REVIEWS, 2010, 110 (08) : 4606 - 4655
[10] Cyclopentadienyl RuII complexes as highly efficient catalysts for the N-methylation of alkylamines by methanol
Del Zotto, A
Baratta, W
Sandri, M
Verardo, G
Rigo, P
[J]. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2004, (03) : 524 - 529

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