Borrowing Hydrogen Mechanism in Amine Alkylation by Single Atom Nickel Catalysts

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11332 - 11342

Published: July 15, 2024

The alkylation of amines with alcohols by borrowing hydrogen (BH) is a versatile synthetic route to various relevant compounds, including drugs and agrochemicals. atom economy this reaction, water as the sole byproduct, entails complex mechanism in which alcohol activation can follow multiple competing pathways. interest single catalysts (SACs) combining advantages homogeneous heterogeneous systems motivated computational study on BH catalyzed nickel SACs. We found that oxidation, charge, spin states system, well geometry support, all have strong influence mechanism. pyrrolic support was most reactive dicationic state nearly degenerate singlet triplet configurations. free energy catalyst hydrogenation H2 strongly correlated its reactivity, thus being useful descriptor. Further, followed an unusual reaction pathway takes delivers H equivalents, metal playing spectator role. This provides insights for further development

Language: Английский

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Acceptorless Dehydrogenative Coupling Reactions by Manganese Pincer Complexes

Asian Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 10(8), P. 1958 - 1985

Published: May 26, 2021

Abstract Acceptorless dehydrogenative coupling reactions has emerged as one of the promising technique in synthetic organic chemistry to construct carbon‐carbon and carbon‐heteroatom bonds an environmentally benign sustainable way. The methodology is highly atom economical produces water hydrogen byproducts. This protocol, coupled with earth‐abundant less toxic manganese catalyst provides a unique opportunity various synthons biologically important motifs. In recent years, tremendous progress been made catalysis based on pincer ligands for homogeneous transformations. review covers field catalyzed acceptorless reactions, their scope brief mechanistic discussion.

Language: Английский

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Enantioselective direct, base-free hydrogenation of ketones by a manganese amido complex of a homochiral, unsymmetrical P–N–P′ ligand

Catalysis Science & Technology, Journal Year: 2021, Volume and Issue: 11(9), P. 3153 - 3163

Published: Jan. 1, 2021

Base-free direct hydrogenation of ketones using a Mn(PNP′)(CO)₂ complex is more enantioselective than that related base-activated iron complex.

Language: Английский

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Selective Transformation of Vicinal Glycols to α-Hydroxy Acetates in Water via a Dehydrogenation and Oxidization Relay Process by a Self-Supported Single-Site Iridium Catalyst

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(21), P. 12833 - 12839

Published: Oct. 7, 2021

α-Hydroxy acids have attracted broad attention because of their prevalence in bioactive molecules and biodegradable polymers, but conventional syntheses are usually restricted to aromatic substrates, especially, a stepwise manner. Herein, we disclose the transformation alkyl aryl vicinal glycols α-hydroxy acetates water under air atmosphere with our solid self-supported NHC-Ir single-site catalyst. Both aliphatic compatible much higher catalytic efficiency presence this catalyst than other viable molecular catalysts (93% vs <35%) "isolation effect". Remarkably, could be reused for 20 runs without an obvious loss activity selectivity. Control experiments density functional theory calculations reveal that reaction firstly undergoes dehydrogenation facilitated by catalyst, then it proceeds through unexpected oxidization relay step oxygen air, leading acetate formation. Our protocol can potentially contribute valorization readily available inexpensive diols.

Language: Английский

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Acceptorless dehydrogenation of primary alcohols to carboxylic acids by self-supported NHC-Ru single-site catalysts

Journal of Catalysis, Journal Year: 2022, Volume and Issue: 408, P. 165 - 172

Published: Feb. 26, 2022

Language: Английский

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