Insights into the Active Sites and Mechanism of Photochemical Synthesis of N-Benzyl-N-Methyl-1-Phenylmethanamine Via Coupling of Benzylamine, Benzaldehyde and Co2 Under Mild Conditions DOI
Suman L. Jain, Anil Malik, Nitish Saini

et al.

Published: Jan. 1, 2023

Herein, we report a combination of experimental and computational studies for the synthesis N-benzyl-N-methyl-1-phenylmethanamine via three component coupling benzylamine, benzaldehyde CO2 under light irradiation as model to understand reaction mechanism optimum conditions that can afford this efficiently. We performed systematic investigation using Density Functional Theory (DFT) revealed formation imine two intermediates (I & II) through with benzyl amine in presence excess amount phenyl saline. The Molecular electrostatic potential activation energy calculations depicted Intermediate I (formoxysilane) by insertion into Si-H bond silane hydrogen bonding. Furthermore, converted II reacting saline (PhSiH3), followed final methylated product C-N between carbon nitrogen group.

Language: Английский

Unleashing Selective Reduction and Reductive Methylation of N-Heterocycles Using Methanol via Strategic Reaction Condition Modulation DOI
Ishani Borthakur,

Srabani Nandi,

Rupsa Pramanick

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3008 - 3022

Published: Feb. 5, 2025

Language: Английский

Citations

1
Direct carbonyl reductive functionalizations by diphenylphosphine oxide DOI Creative Commons

Feng Liu,

Jianyu Dong, Ruofei Cheng

et al.

Science Advances, Journal Year: 2025, Volume and Issue: 11(6)

Published: Feb. 7, 2025

Reductive functionalization of aldehydes and ketones is one the most challenging but ultimately rewarding areas in synthetic chemistry related sciences. We report a simple extremely versatile carbonyl reductive strategy achieving direct, highly selective, efficient amination, etherification, esterification, phosphinylation reactions (hetero)aryl ketones, which are or unattainable to achieve by traditional strategies, using only diphenylphosphine oxide an inorganic base. It enables modular synthesis functionally structurally diverse tertiary amines, ethers, esters, phosphine oxides, etc., as well pesticides, drug intermediates, pharmaceuticals. Compared phosphorus-mediated name reactions, this firstly transformed C═O bonds into C-element single bonds. Mechanistically, phosphinates formed undergo unconventional nucleophilic substitution at C atom within their C─O─P unit. Thus, work provides important strides field aldehydes/ketones, transformation, various fundamental reactions.

Language: Английский

Citations

1
Selective Transfer Hydrogenation of C=O and Conjugated C=C Bonds Using An NHC‐Based Pincer (CNC)MnI Complex in Methanol** DOI
Adarsha Mandal,

Kasturi Ganguli,

Manoj Pradhan

et al.

ChemSusChem, Journal Year: 2023, Volume and Issue: 16(18)

Published: June 8, 2023

Base metal catalyzed transfer hydrogenation reactions using methanol is highly challenging. Employing a single N-heterocyclic carbene (NHC)-based pincer (CNC)MnI complex, chemoselective and double of α, β-unsaturated ketones to saturated or alcohols by utilizing as the hydrogen source disclosed. The protocol was tolerant towards selective C=C C=O bonds in presence several other reducible functional groups led synthesis biologically relevant molecules natural products. Notably, this first report Mn-catalyzed carbonyl with methanol. Several control experiments, kinetic studies, Hammett density theory (DFT) calculations were carried out understand mechanistic details catalytic process.

Language: Английский

Citations

15
Utilization of methanol for condensation interrupted chemoselective transfer hydrogenation of CC, CO, and CN bonds under low catalyst loading DOI

Anirban Sau,

Divya Mahapatra,

Sadhan Dey

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(9), P. 2274 - 2286

Published: Jan. 1, 2023

Selective transfer hydrogenation (TH) of unsaturated molecules using methanol is challenging as the in situ generated formaldehyde prone to react with active methylene ( C -methylation) or amine N core desired product.

Language: Английский

Citations

12
2-(2-Benzimidazolyl)pyridine Mn(I) Complexes: Synthesis and Exploration of Catalytic Activity toward Synthesis of Pyrimidine and Quinoline DOI

Srabani Nandi,

Ishani Borthakur,

Kasturi Ganguli

et al.

Organometallics, Journal Year: 2023, Volume and Issue: 42(14), P. 1793 - 1802

Published: May 11, 2023

A series of phosphine-free benzimidazole and pyridine-containing bidentate Mn(I) complexes were synthesized. Among them, Mn1 complex bearing a proton-responsive 2-hydroxypyridine-appended ligand was found to be highly effective for the synthesis different N-heterocycles utilizing alcohols. Employing significantly lower catalyst loading (0.05 mol %), several substituted pyrimidines quinolines effectively The lactim–lactam acid–base equilibrium 2-hydroxypyridine fragment, role countercation base, effect externally added ligands investigated. probable catalytic cycle proposed based on basis various control experiments kinetic studies.

Language: Английский

Citations

12
Reductive Aminomethylation Using Ammonium Formate and Methanol as N1 and C1 Source: Direct Synthesis of Mono- and Di-Methylated Amines DOI
Ishani Borthakur,

Srabani Nandi,

Yuvraj Bilora

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 5847 - 5857

Published: April 2, 2024

An Ir(III) complex catalyzed single and dual reductive amination followed by N-methylation of aldehydes ketones to synthesize N,N-dimethyl as well N-methyl tertiary amines, respectively, utilizing ammonium formate methanol N1 C1 sources is reported. The protocol was efficiently extended a tandem amination/N-methylation/cyclization keto acids/esters leading lactams. A broad substrate scope, synthesis bioactive molecules, also demonstrated. Control experiments, kinetic studies, DFT calculations were performed based on which plausible mechanism proposed.

Language: Английский

Citations

3
N,N-Dialkylation of Acyl Hydrazides with Alcohols Catalyzed by Amidato Iridium Complexes via Borrowing Hydrogen DOI
Wan‐Hui Wang,

Wei‐Yu Shao,

Jia-Yue Sang

et al.

Organometallics, Journal Year: 2023, Volume and Issue: 42(18), P. 2623 - 2631

Published: April 1, 2023

Direct N,N-dialkylation of acyl hydrazide catalyzed by a series amidato iridium complexes bearing an electron-donating group in the ligand using methanol or ethanol as alkyl reagent under weak base conditions (10 mol % KHCO3) is described. A wide range derivatives are converted to corresponding N,N-dialkylated products excellent yields (38 examples, ≤96%). On basis control experiments and nuclear magnetic resonance studies, plausible mechanism was proposed. The experimental results indicate that ortho groups on phenyl moiety picolinamide play crucial role catalytic activity.

Language: Английский

Citations

4
Half-sandwich ruthenium complexes with acylhydrazone ligands: synthesis and catalytic activity in the N-alkylation of hydrazides DOI
Heng Li, Ke Wang, Lin Yang

et al.

Dalton Transactions, Journal Year: 2023, Volume and Issue: 53(6), P. 2797 - 2806

Published: Dec. 29, 2023

Novel half-sandwich ruthenium complexes termed [(

Language: Английский

Citations

4
Synthesis and catalytic activity of half‐sandwich iridium complexes with acylhydrazone ligands for N‐alkylation of hydrazides under mild conditions DOI
Ke Wang, Song Gao, Yu‐Zhou Luo

et al.

Applied Organometallic Chemistry, Journal Year: 2024, Volume and Issue: 38(6)

Published: April 14, 2024

A new [Cp*IrClL] half‐sandwich iridium complex was successfully synthesized by coordinating an acylhydrazone ligand with [Cp*IrCl 2 ] , followed comprehensive characterization using various spectroscopic and analytical techniques. Complex 3 subjected to crystal structure analysis, revealing that the coordinates through bidentate coordination involving imidolate oxygen imine nitrogen atoms. This interaction resulted in formation of a pseudo ‐octahedral geometry center. The complexes 1 – 4 which are stable presence air moisture, exhibit significant catalyst performance N‐alkylation reactions hydrazides under gentle reaction conditions. catalyzes types alcohols undergo acyl via one‐pot method, yielding diverse N‐alkylated hydrazide derivatives. displayed exceptional catalytic efficiency, broad variety substrates, conditions, indicating its potential for industrial applications.

Language: Английский

Citations

1
Regioselective Ring Opening of Epoxide with Alcohols: A Selective Route to α‐Alkylated Ketones and β‐Alkylated Secondary Alcohols DOI

Srabani Nandi,

Ishani Borthakur, Adarsha Mandal

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(16)

Published: April 17, 2024

Abstract Herein, we demonstrated an effective protocol for the regioselective ring opening of epoxides with alcohols. By following this strategy, both α‐alkylated ketones and β‐alkylated secondary alcohols were selectively obtained by changing reaction parameters. Compared to previously reported protocols, methodology was operated using considerably lower base at temperature. Notably, a wide array substrates tolerance different functional groups demonstrated. A series control experiments deuterium‐labelling performed understand catalytic process.

Language: Английский

Citations

1