Development of catalytic nitrogen fixation using transition metal–dinitrogen complexes under mild reaction conditions

2018 ◽  
Vol 47 (33) ◽  
pp. 11290-11297 ◽  
Author(s):  
Yoshiaki Nishibayashi
Keyword(s):  
Nitrogen Fixation ◽  
Transition Metal ◽  
Recent Progress ◽  
Reaction Conditions ◽  
Dinitrogen Complexes

This paper describes our recent progress in catalytic nitrogen fixation using transition metal–dinitrogen complexes as catalysts.

Development of Catalytic Conversion of Nitrogen Molecule into Ammonia Using Molybdenum Complexes under Ambient Reaction Conditions

2021 ◽  
Author(s):  
Yuya Ashida ◽  
Yoshiaki Nishibayashi
Keyword(s):  
Nitrogen Fixation ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Catalytic Conversion ◽  
Nitrogen Molecule ◽  
Reaction Conditions ◽  
Molybdenum Complexes

Nitrogen fixation using homogeneous transition metal complexes under mild reaction conditions is a challenging topic in the field of chemistry. Several successful examples of the catalytic conversion of nitrogen molecule...

scholarly journals Ammonia Formation Catalyzed by Dinitrogen-Bridged Dirhenium Complex Bearing PNP-Pincer Ligands under Mild Reaction Conditions

2020 ◽  
Author(s):  
Fanqiang Meng ◽  
Shogo Kuriyama ◽  
Hiromasa Tanaka ◽  
Akihito Egi ◽  
Kazunari Yoshizawa ◽  
...  
Keyword(s):  
Nitrogen Fixation ◽  
Pincer Ligands ◽  
Pincer Ligand ◽  
Reaction Conditions ◽  
Rhenium Atom ◽  
Phosphine Complexes ◽  
Proton Source ◽  
Dinitrogen Complexes ◽  
Dinitrogen Complex ◽  
Ammonia Formation

A series of rhenium complexes bearing a pyridine-based PNP-type pincer ligand are synthesized from rhenium phosphine complexes as precursors. A dinitrogen-bridged dirhenium complex bearing the PNP-type pincer ligands catalytically converts dinitrogen into ammonia in the reaction with KC<sub>8</sub> as a reductant and [HPCy<sub>3</sub>]BAr<sup>F</sup><sub>4</sub> (Cy = cyclohexyl, Ar<sup>F</sup> = 3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) as a proton source at –78 °C to afford 8.4 equiv of ammonia based on the rhenium atom of the catalyst. The rhenium-dinitrogen complex also catalyzes silylation of dinitrogen in the reaction with KC<sub>8</sub> as a reductant and Me<sub>3</sub>SiCl as a silylating reagent under ambient reaction conditions to afford 11.3 equiv of tris(trimethylsilyl)amine based on the rhenium atom of the catalyst. These results demonstrate the first successful example of catalytic nitrogen fixation under mild reaction conditions by using rhenium-dinitrogen complexes as catalysts.

scholarly journals Ammonia Formation Catalyzed by Dinitrogen-Bridged Dirhenium Complex Bearing PNP-Pincer Ligands under Mild Reaction Conditions

2020 ◽  
Author(s):  
Fanqiang Meng ◽  
Shogo Kuriyama ◽  
Hiromasa Tanaka ◽  
Akihito Egi ◽  
Kazunari Yoshizawa ◽  
...  
Keyword(s):  
Nitrogen Fixation ◽  
Pincer Ligands ◽  
Pincer Ligand ◽  
Reaction Conditions ◽  
Rhenium Atom ◽  
Phosphine Complexes ◽  
Proton Source ◽  
Dinitrogen Complexes ◽  
Dinitrogen Complex ◽  
Ammonia Formation

A series of rhenium complexes bearing a pyridine-based PNP-type pincer ligand are synthesized from rhenium phosphine complexes as precursors. A dinitrogen-bridged dirhenium complex bearing the PNP-type pincer ligands catalytically converts dinitrogen into ammonia in the reaction with KC<sub>8</sub> as a reductant and [HPCy<sub>3</sub>]BAr<sup>F</sup><sub>4</sub> (Cy = cyclohexyl, Ar<sup>F</sup> = 3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) as a proton source at –78 °C to afford 8.4 equiv of ammonia based on the rhenium atom of the catalyst. The rhenium-dinitrogen complex also catalyzes silylation of dinitrogen in the reaction with KC<sub>8</sub> as a reductant and Me<sub>3</sub>SiCl as a silylating reagent under ambient reaction conditions to afford 11.3 equiv of tris(trimethylsilyl)amine based on the rhenium atom of the catalyst. These results demonstrate the first successful example of catalytic nitrogen fixation under mild reaction conditions by using rhenium-dinitrogen complexes as catalysts.

Direct Cyclization of Alkenyl Thioester via Transition Metal‐hydrogen Atom Transfer/radical‐polar Crossover Mechanism

2019 ◽  
Author(s):  
Shiori Date ◽  
Kensei Hamasaki ◽  
Karen Sunagawa ◽  
Hiroki Koyama ◽  
Chikayoshi Sebe ◽  
...  
Keyword(s):  
Natural Products ◽  
Hydrogen Atom ◽  
Transition Metal ◽  
Hydrogen Atom Transfer ◽  
Synthetic Method ◽  
Atom Transfer ◽  
Reaction Conditions ◽  
Hydride Hydrogen ◽  
Sulfur Heterocycles ◽  
One Step

<div>We report here a catalytic, Markovnikov selective, and scalable synthetic method for the synthesis of saturated sulfur heterocycles, which are found in the structures of pharmaceuticals and natural products, in one step from an alkenyl thioester. Unlike a potentially labile alkenyl thiol, an alkenyl thioester is stable and easy to prepare. The powerful Co catalysis via a cobalt hydride hydrogen atom transfer and radical-polar crossover mechanism enabled simultaneous cyclization and deprotection. The substrate scope was expanded by the extensive optimization of the reaction conditions and tuning of the thioester unit.</div>

The chemistry of 4-(dicyanomethylene)-3-methyl-l-phenyl-2-pyrazoline-5- ones as a privileged scaffold in synthesis of heterocycles

2020 ◽  
Vol 17 ◽  
Author(s):  
Mohsen A.-M. Gomaa ◽  
Huda A. Ali
Keyword(s):  
Building Block ◽  
Heterocyclic Compounds ◽  
Recent Progress ◽  
Reaction Conditions ◽  
Azacrown Ethers ◽  
Wide Range ◽  
Privileged Scaffold ◽  
Number Of Publications ◽  
Near Future

Background : The reactivity of 4-(dicyanomethylene)-3-methyl-l-phenyl-2-pyrazoline-5-one DCNP 1 and its derivatives makes it valuable as a building block for the synthesis of heterocyclic compounds like pyrazolo-imidazoles, - thiazoles, spiropyridines, spiropyrroles, spiropyrans and others. As a number of publications have reported on the reactivity of DCNP and its derivatives, we compiled some features of this interesting molecule. Objective: This article aims to review the preparation of DCNP, its reactivity and application in heterocyclic and dyes synthesis. Conclusion: In this review we have provided an overview of recent progress in the chemistry of DCNP and its significance in synthesis of various classes of heterocyclic compounds and dyes. The unique reactivity of DCNP offers unprecedentedly mild reaction conditions for the generation of versatile cynomethylene dyes from a wide range of precursors including amines, α-aminocarboxylic acids, their esters, phenols, malononitriles and azacrown ethers. We anticipate that more innovative transformations involving DCNP will continue to emerge in the near future.

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