Double Dehydrogenation of Primary Amines to Nitriles by a Ruthenium Complex Featuring Pyrazole Functionality

被引：94

作者：

Dutta, Indranil ^{[1
,2
]}

Yadav, Sudhir ^{[1
,2
]}

Sarbajna, Abir ^{[1
,2
]}

De, Subhabrata ^{[1
,2
]}

Hoelscher, Markus ^{[3
]}

Leitner, Walter ^{[3
,4
]}

Bera, Jitendra K. ^{[1
,2
]}

机构：

[1] Indian Inst Technol Kanpur, Dept Chem, Kanpur 208016, Uttar Pradesh, India

[2] Indian Inst Technol Kanpur, Ctr Environm Sci & Engn, Kanpur 208016, Uttar Pradesh, India

[3] Rhein Westfal TH Aachen, Inst Tech & Makromol Chem, Worringerweg 2, D-52074 Aachen, Germany

[4] Max Planck Inst Chem Energy Convers, Stiftstr 34-36, D-45470 Mulheim, Germany

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 28期

关键词：

METAL-LIGAND COOPERATION; CATALYTIC INTRAMOLECULAR HYDROAMINATION; N-HETEROCYCLIC CARBENE; PCP PINCER COMPLEXES; ACCEPTORLESS DEHYDROGENATION; SECONDARY-AMINES; BOND ACTIVATION; AROMATIZATION-DEAROMATIZATION; IRIDIUM COMPLEXES; AEROBIC OXIDATION;

D O I：

10.1021/jacs.8b05009

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A ruthenium(II) complex bearing a naphthyridine-functionalized pyrazole ligand catalyzes oxidant free and acceptorless selective double dehydrogenation of primary amines to nitriles at moderate temperature. The role of the proton-responsive entity on the ligand scaffold is demonstrated by control experiments, including the use of a N-methylated pyrazole analogue. DFT calculations reveal intricate hydride and proton transfers to achieve the overall elimination of 2 equiv of H-2.

引用

页码：8662 / 8666

页数：5

共 75 条

[1] Isolation and interconversion of protic N-heterocyclic carbene and imidazolyl complexes:: Application to catalytic dehydrative condensation of N-(2-pyridyl)benzimidazole and allyl alcohol [J].

Araki, Kenjirou ;

Kuwata, Shigeki ;

Ikariya, Takao .

ORGANOMETALLICS, 2008, 27 (10) :2176-2178

[2] Catalysed aerobic dehydrogenation of amines and an X-ray crystal structure of a bis(benzylamine) ruthenium(II) porphyrin species [J].

Bailey, AJ ;

James, BR .

CHEMICAL COMMUNICATIONS, 1996, (20) :2343-2344

[3] Kinetics and mechanism of iridium-catalyzed dehydrogenation of primary amines to nitriles [J].

Bernskoetter, Wesley H. ;

Brookhart, Maurice .

ORGANOMETALLICS, 2008, 27 (09) :2036-2045

[4] A Single Nickel Catalyst for the Acceptorless Dehydrogenation of Alcohols and Hydrogenation of Carbonyl Compounds [J].

Chakraborty, Sumit ;

Piszel, Paige E. ;

Brennessel, William W. ;

Jones, William D. .

ORGANOMETALLICS, 2015, 34 (21) :5203-5206

[5] Well-Defined Iron Catalysts for the Acceptor less Reversible Dehydrogenation-Hydrogenation of Alcohols and Ketones [J].

Chakraborty, Sumit ;

Lagaditis, Paraskevi O. ;

Foerster, Moritz ;

Bielinski, Elizabeth A. ;

Hazari, Nilay ;

Holthausen, Max C. ;

Jones, William D. ;

Schneider, Sven .

ACS CATALYSIS, 2014, 4 (11) :3994-4003

[6] A Robust Nickel Catalyst for Cyanomethylation of Aldehydes: Activation of Acetonitrile under Base-Free Conditions [J].

Chakraborty, Sumit ;

Patel, Yogi J. ;

Krause, Jeanette A. ;

Guan, Hairong .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (29) :7523-7526

[7] Homogeneous Transition Metal Catalysis of Acceptorless Dehydrogenative Alcohol Oxidation: Applications in Hydrogen Storage and to Heterocycle Synthesis [J].

Crabtree, Robert H. .

CHEMICAL REVIEWS, 2017, 117 (13) :9228-9246

[8] Resolving Heterogeneity Problems and Impurity Artifacts in Operationally Homogeneous Transition Metal Catalysts [J].

Crabtree, Robert H. .

CHEMICAL REVIEWS, 2012, 112 (03) :1536-1554

[9] A Highly Efficient Catalyst for Selective Oxidative Scission of Olefins to Aldehydes: Abnormal-NHC-Ru(II) Complex in Oxidation Chemistry [J].

Daw, Prosenjit ;

Petakamsetty, Ramu ;

Sarbajna, Abir ;

Laha, Siladitya ;

Ramapanicker, Ramesh ;

Bera, Jitendra K. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (40) :13987-13990

[10] Dehydrogenation as a Substrate-Activating Strategy in Homogeneous Transition-Metal Catalysis [J].

Dobereiner, Graham E. ;

Crabtree, Robert H. .

CHEMICAL REVIEWS, 2010, 110 (02) :681-703

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