Oxidant-Free Conversion of Primary Amines to Nitriles

Tseng, Kuei Nin T.; Rizzi, Andrew; Szymczak, Nathaniel K.

doi:10.1021/ja409223a

Cited by 145 publications

(82 citation statements)

References 69 publications

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“…CN bond dehydrogenation : In 2013, Szymczak and co‐workers reported the double dehydrogenation of amines to synthesize nitriles isolated in yields of 17–75 % 89. With their system, even sensitive compounds could be dehydrogenated selectively.…”

Section: Catalysis With Pincer‐type Catalystsmentioning

confidence: 99%

Pincer‐Type Complexes for Catalytic (De)Hydrogenation and Transfer (De)Hydrogenation Reactions: Recent Progress

Werkmeister

Neumann

Junge

et al. 2015

Chemistry A European J

328

144

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Pincer complexes are becoming increasingly important for organometallic chemistry and organic synthesis. Since numerous applications for such catalysts have been developed in recent decades, this Minireview covers progress in their use as catalysts for (de)hydrogenation and transfer (de)hydrogenation reactions during the last four years. Aside from noble-metal-based pincer complexes, the corresponding base metal complexes are also highlighted and their applications summarized.

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Section: Catalysis With Pincer‐type Catalystsmentioning

confidence: 99%

Pincer‐Type Complexes for Catalytic (De)Hydrogenation and Transfer (De)Hydrogenation Reactions: Recent Progress

Werkmeister

Neumann

Junge

et al. 2015

Chemistry A European J

328

144

View full text Add to dashboard Cite

show abstract

“…[17][18][19][20] In this sense, the technological problems are minimized as the actuali nfrastructure is basedi nl iquidsf or storage and transport. [29] The viabilityo ft he amine/nitrile pair as ap otentialo rganic hydrogen carrier also lies in the effectiveness of the reverse process, that is, the hydrogenation of nitriles. [23][24][25][26][27] In this work, we have evaluatedt he potential of the amine/nitrile paira saliquid organic hydrogen carrier,a s suggested by Grelliera nd Sabo-Etienne in af rontier-type article (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Catalytic Hydrogen Production by Ruthenium Complexes from the Conversion of Primary Amines to Nitriles: Potential Application as a Liquid Organic Hydrogen Carrier

Ventura‐Espinosa

Marzá-Beltrán

Mata

2016

Chemistry A European J

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The potential application of the primary amine/nitrile pair as a liquid organic hydrogen carrier (LOHC) has been evaluated. Ruthenium complexes of formula [(p-cym)Ru(NHC)Cl ] (NHC=N-heterocyclic carbene) catalyze the acceptorless dehydrogenation of primary amines to nitriles with the formation of molecular hydrogen. Notably, the reaction proceeds without any external additive, under air, and under mild reaction conditions. The catalytic properties of a ruthenium complex supported on the surface of graphene have been explored for reutilization purposes. The ruthenium-supported catalyst is active for at least 10 runs without any apparent loss of activity. The results obtained in terms of catalytic activity, stability, and recyclability are encouraging for the potential application of the amine/nitrile pair as a LOHC. The main challenge in the dehydrogenation of benzylamines is the selectivity control, such as avoiding the formation of imine byproducts due to transamination reactions. Herein, selectivity has been achieved by using long-chain primary amines such as dodecylamine. Mechanistic studies have been performed to rationalize the key factors involved in the activity and selectivity of the catalysts in the dehydrogenation of amines. The experimental results suggest that the catalyst resting state contains a coordinated amine.

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“…Thereafter, Hong and Muthaiah reported that ruthenium hydride complexes, such as RuH 2 (CO)(PPh 3 ) 3 and Shvo's complex, are also effective catalysts for the dehydrogenation of N‐containing heterocycles, under “acceptorless” and base‐free conditions . Later, a very interesting result was published by Szymczak's group where they demonstrated an amide‐derived NNN‐Ru II hydride complex catalyzes the oxidant‐free, acceptorless, and chemoselective dehydrogenation of primary and secondary amines to the corresponding nitriles and imines with the liberation of dihydrogen . However, dehydrogenation of amines with these ruthenium hydride complexes rely on the basic principle of hydrogen‐borrowing, and are mechanistically different from the aerobic oxidation of amines.…”

Section: Nitriles and Iminesmentioning

confidence: 99%

Ruthenium‐Catalyzed Aerobic Oxidation of Amines

Ray

Hazari

Lahiri

et al. 2018

Chemistry An Asian Journal

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Amine oxidation is one of the fundamental reactions in organic synthesis as it leads to a variety of value-added products such as oximes, nitriles, imines, and amides among many others. These products comprise the key N-containing building blocks in the modern chemical industry, and such transformations, when achieved in the presence of molecular oxygen without using stoichiometric oxidants, are much preferred as they circumvent the production of unwanted wastes. In parallel, the versatility of ruthenium catalysts in various oxidative transformations is well-documented. Herein, this review focuses on aerobic oxidation of amines specifically by using ruthenium catalysts and highlights the major achievements in this direction and challenges that still need to be addressed.

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Oxidant-Free Conversion of Primary Amines to Nitriles

Cited by 145 publications

References 69 publications

Pincer‐Type Complexes for Catalytic (De)Hydrogenation and Transfer (De)Hydrogenation Reactions: Recent Progress

Pincer‐Type Complexes for Catalytic (De)Hydrogenation and Transfer (De)Hydrogenation Reactions: Recent Progress

Catalytic Hydrogen Production by Ruthenium Complexes from the Conversion of Primary Amines to Nitriles: Potential Application as a Liquid Organic Hydrogen Carrier

Ruthenium‐Catalyzed Aerobic Oxidation of Amines

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