scholarly journals Tungsten-Catalyzed Direct N-Alkylation of Amines with Alcohols

2020 ◽  
Author(s):  
Xiao-Bing Lan ◽  
Zongren Ye ◽  
Weikang Li ◽  
Jiahao Liu ◽  
Ming Huang ◽  
...  
Keyword(s):  
Homogeneous Catalysis ◽  
Alkylation Reaction ◽  
Synthetic Method ◽  
Computational Studies ◽  
Primary Alcohols ◽  
Major Goal ◽  
Earth Abundant ◽  
Borrowing Hydrogen ◽  
Hydrogen Autotransfer

The implementation of earth-abundant metals mediated chemistry is a major goal in homogeneous catalysis. Borrowing hydrogen/hydrogen autotransfer (BH/HA) reaction, as a straightforward and sustainable synthetic method, has attracted considerable attention in the development of earth-abuandant metal catalysts. Herein, we report a tungsten-catalyzed <i>N</i>-alkylation reaction of amines with primary alcohols via BH/HA. This phosphine-free W(phen)(CO)<sub>4</sub> (phen=1,10-phenthroline) system was demonstrated as a practical and easily accessible <i>in-situ</i> catalysis for a broad range of amines and alcohols (up to 49 examples, including 16 previously undisclosed products). Notably, this tungsten system can tolerate numerous functional groups, especially the challenging substrates with sterically hindered substituents, or heteroatoms. Mechanistic insights based on experimental and computational studies are also provided.

scholarly journals Tungsten-Catalyzed Direct N-Alkylation of Amines with Alcohols

2020 ◽  
Author(s):  
Xiao-Bing Lan ◽  
Zongren Ye ◽  
Weikang Li ◽  
Jiahao Liu ◽  
Ming Huang ◽  
...  
Keyword(s):  
Homogeneous Catalysis ◽  
Alkylation Reaction ◽  
Synthetic Method ◽  
Computational Studies ◽  
Primary Alcohols ◽  
Major Goal ◽  
Earth Abundant ◽  
Borrowing Hydrogen ◽  
Hydrogen Autotransfer

The implementation of earth-abundant metals mediated chemistry is a major goal in homogeneous catalysis. Borrowing hydrogen/hydrogen autotransfer (BH/HA) reaction, as a straightforward and sustainable synthetic method, has attracted considerable attention in the development of earth-abuandant metal catalysts. Herein, we report a tungsten-catalyzed <i>N</i>-alkylation reaction of amines with primary alcohols via BH/HA. This phosphine-free W(phen)(CO)<sub>4</sub> (phen=1,10-phenthroline) system was demonstrated as a practical and easily accessible <i>in-situ</i> catalysis for a broad range of amines and alcohols (up to 49 examples, including 16 previously undisclosed products). Notably, this tungsten system can tolerate numerous functional groups, especially the challenging substrates with sterically hindered substituents, or heteroatoms. Mechanistic insights based on experimental and computational studies are also provided.

Ruthenium(II) Complexes with N-Heterocyclic Carbene-Phosphine Ligands for the N-Alkylation of Amines with Alcohols

2021 ◽  
Author(s):  
Ming Huang ◽  
Yinwu Li ◽  
Xiao-Bing Lan ◽  
Jiahao Liu ◽  
Cunyuan Zhao ◽  
...  
Keyword(s):  
Metal Hydride ◽  
Phosphine Ligands ◽  
Hydride Complexes ◽  
Borrowing Hydrogen ◽  
Hydrogen Autotransfer

Metal hydride complexes are key intermediates for N-alkylation of amines with alcohols by borrowing hydrogen/hydrogen autotransfer (BH/HA) strategy. Reactivity tuning of metal hydride complexes could adjust the dehydrogenation of alcohols...

scholarly journals A cross-dehydrogenative C(sp3)−H heteroarylation via photo-induced catalytic chlorine radical generation

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Chia-Yu Huang ◽  
Jianbin Li ◽  
Chao-Jun Li
Keyword(s):  
Hydrogen Atom ◽  
Hydrogen Evolution ◽  
Alkyl Radical ◽  
Cobalt Catalyst ◽  
Alkylation Reaction ◽  
Hydrogen Atom Abstraction ◽  
Dehydrogenative Coupling ◽  
Radical Generation ◽  
Limited Scope

AbstractHydrogen atom abstraction (HAT) from C(sp3)–H bonds of naturally abundant alkanes for alkyl radical generation represents a promising yet underexplored strategy in the alkylation reaction designs since involving stoichiometric oxidants, excessive alkane loading, and limited scope are common drawbacks. Here we report a photo-induced and chemical oxidant-free cross-dehydrogenative coupling (CDC) between alkanes and heteroarenes using catalytic chloride and cobalt catalyst. Couplings of strong C(sp3)–H bond-containing substrates and complex heteroarenes, have been achieved with satisfactory yields. This dual catalytic platform features the in situ engendered chlorine radical for alkyl radical generation and exploits the cobaloxime catalyst to enable the hydrogen evolution for catalytic turnover. The practical value of this protocol was demonstrated by the gram-scale synthesis of alkylated heteroarene with merely 3 equiv. alkane loading.

scholarly journals Selective hydroboration of unsaturated bonds by an easily accessible heterotopic cobalt catalyst

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Chuhan Li ◽  
Shuo Song ◽  
Yuling Li ◽  
Chang Xu ◽  
Qiquan Luo ◽  
...  
Keyword(s):  
Base Metal ◽  
Large Scale ◽  
Metal Cluster ◽  
Active Species ◽  
Cobalt Catalysts ◽  
Metal Salts ◽  
One Pot ◽  
Practical Utilization ◽  
Earth Abundant

AbstractHomogeneous earth-abundant metal catalysis based on well-defined molecular complexes has achieved great advance in synthetic methodologies. However, sophisticated ligand, hazardous activator and multistep synthesis starting from base metal salts are generally required for the generation of active molecular catalysts, which may hinder their broad application in large scale organic synthesis. Therefore, the development of metal cluster catalysts formed in situ from simple earth-abundant metal salts is of importance for the practical utilization of base metal resource, yet it is still in its infancy. Herein, a mixture of catalytic amounts of cobalt (II) iodide and potassium tert-butoxide is discovered to be highly active for selective hydroboration of vinylarenes and dihydroboration of nitriles, affording a good yield of diversified hydroboration products that without isolation can readily undergo further one pot transformations. It should be highlighted that the alkoxide-pinacolborane combination acts as an efficient activation strategy to activate cobalt (II) iodide for the generation of metastable heterotopic cobalt catalysts in situ, which is proposed to be catalytically active species.

scholarly journals Toward a mechanistic understanding of electrocatalytic nanocarbon

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Erik J. Askins ◽  
Marija R. Zoric ◽  
Matthew Li ◽  
Zhengtang Luo ◽  
Khalil Amine ◽  
...  
Keyword(s):  
Spectroscopic Studies ◽  
Synthetic Methods ◽  
Computational Studies ◽  
Molecular Models ◽  
Chemical Production ◽  
True Nature ◽  
Catalytic Mechanisms ◽  
Mechanistic Understanding ◽  
Further Development

AbstractElectrocatalytic nanocarbon (EN) is a class of material receiving intense interest as a potential replacement for expensive, metal-based electrocatalysts for energy conversion and chemical production applications. The further development of EN will require an intricate knowledge of its catalytic behaviors, however, the true nature of their electrocatalytic activity remains elusive. This review highlights work that contributed valuable knowledge in the elucidation of EN catalytic mechanisms. Experimental evidence from spectroscopic studies and well-defined molecular models, along with the survey of computational studies, is summarized to document our current mechanistic understanding of EN-catalyzed oxygen, carbon dioxide and nitrogen electrochemistry. We hope this review will inspire future development of synthetic methods and in situ spectroscopic tools to make and study well-defined EN structures.

Combining Experimental and Computational Studies to Understand and Predict Reactivities of Relevance to Homogeneous Catalysis

2014 ◽  
Vol 20 (50) ◽  
pp. 16432-16441 ◽  
Author(s):  
Althea S.-K. Tsang ◽  
Italo A. Sanhueza ◽  
Franziska Schoenebeck
Keyword(s):  
Homogeneous Catalysis ◽  
Computational Studies

scholarly journals Ammonothermal Synthesis of Earth-Abundant Nitride Semiconductors ZnSiN2 and ZnGeN2 and Dissolution Monitoring by In Situ X-ray Imaging

2017 ◽  
Vol 23 (50) ◽  
pp. 12275-12282 ◽  
Author(s):  
Jonas Häusler ◽  
Saskia Schimmel ◽  
Peter Wellmann ◽  
Wolfgang Schnick
Keyword(s):  
Nitride Semiconductors ◽  
X Ray ◽  
X Ray Imaging ◽  
Earth Abundant

scholarly journals Experimental and Computational Studies on N-alkylation Reaction of N-Benzoyl 5-(Aminomethyl)Tetrazole

Chemistry ◽  
2021 ◽  
Vol 3 (3) ◽  
pp. 704-713
Author(s):  
Younas Aouine ◽  
Aaziz Jmiai ◽  
Anouar Alami ◽  
Abdallah El Asri ◽  
Souad El Issami ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Nmr Spectroscopy ◽  
Density Functional ◽  
Computational Study ◽  
Benzyl Bromide ◽  
13C Nmr Spectroscopy ◽  
Alkylation Reaction ◽  
Computational Studies ◽  
Functional Theory ◽  
1H And 13C Nmr

The N-alkylation reaction of N-benzoyl 5-(aminomethyl)tetrazole (5-AMT) with benzyl bromide was carried out in the presence of K2CO3 as a base. Two separable regioisomers were obtained, thus their purification led to determine the proportion of each of them, and their structures were attributed essentially based on 1H and 13C NMR spectroscopy in addition to the elemental analysis and MS data. In order to confirm the results obtained at the synthesis level, a computational study was carried out by application of density functional theory (DFT) using the Becke three-parameter hybrid exchange functional and the Lee-Yang-Parr correlation functional (B3LYP).

Sign in / Sign up

Export Citation Format

Share Document