Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(9), P. 6078 - 6144

Published: April 17, 2024

Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods their functionalization require them to first be converted into a more activated derivative, while recent years have seen vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can used toward this goal. These broadly classified three categories. Deoxygenative functionalizations, representing derivatization C–O bond, enable alcohol act as leaving group formation new C–C bonds. Etherifications, characterized by O–H represent classical reactivity has been modernized include mild reaction conditions, diverse partners, high selectivities. Lastly, chain reactions described, wherein acts mediator formal C–H alkyl backbone. Each these classes transformation will discussed context intermolecular arylation, alkylation, related reactions, illustrating alcohols harnessed

Language: Английский

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Manganese‐Catalyzed Mono‐N‐Methylation of Aliphatic Primary Amines without the Requirement of External High‐Hydrogen Pressure

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Feb. 1, 2024

Abstract The synthesis of mono‐ N ‐methylated aliphatic primary amines has traditionally been challenging, requiring noble metal catalysts and high‐pressure H 2 for achieving satisfactory yields selectivity. Herein, we developed an approach the selective coupling methanol amines, without hydrogen, using a manganese‐based catalyst. Remarkably, up to 98 % with broad substrate scope were achieved at low catalyst loadings. Notably, due weak base‐catalyzed alcoholysis formamide intermediates, our novel protocol not only obviates addition but also prevents side secondary ‐methylation, supported by control experiments density functional theory calculations.

Language: Английский

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Tailoring metal complexes with N-heterocyclic carbene ligands using Electron-Withdrawing Groups: Impact on catalytic activity and property development

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 516, P. 215897 - 215897

Published: May 28, 2024

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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Dehydroxylative Alkylation of α‐Hydroxy Carboxylic Acid Derivatives via a Spin‐Center Shift

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(25)

Published: April 7, 2022

Abstract A strategically distinct dehydroxylative alkylation reaction of α‐hydroxy carboxylic acid derivatives with alkenes is developed. The starts the attack a 4‐dimethylaminopyridine (DMAP)‐boryl radical to carbonyl oxygen atom, followed by spin‐center shift (SCS) trigger C−O bond scission. resulting α‐carbonyl radicals couple wide range furnish various alkylated products. This strategy allows for efficient conversion array amides and esters derived from several biomass molecules natural products value‐added compounds. Experimental computational studies verified mechanism.

Language: Английский

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Direct α-C–H alkylation of alcohols via photoinduced hydrogen atom transfer

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: 23(10), P. 2365 - 2369

Published: Jan. 1, 2025

A general approach for the α-C-H alkylation of alcohols has been established, offering access to highly functionalized via visible light irradiation with TBAP as a co-catalyst. The methodology exhibits excellent functional group tolerance and wide substrate scope. Its practicality is underscored by successful gram-scale synthesis sunlight-driven reaction demonstration.

Language: Английский

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Iridium-Catalyzed Monoamination of Polyols toward Amino Alcohols or Amino Acids

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8049 - 8059

Published: April 30, 2025

Language: Английский

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Selective Modular Synthesis of ortho-Substituted Phenols via Pd-Catalyzed Dehydrogenation–Coupling–Aromatization of Alcohols

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(9), P. 6222 - 6229

Published: April 21, 2023

Phenols are pivotal precursors and core motifs for various fine chemicals, bioactive molecules, functional materials, among which the site-selective syntheses of ortho-substituted phenols very attractive challenging. Here, we present a palladium-catalyzed dehydrogenation–coupling–aromatization protocol to access from cyclohexanols with primary alcohols. Broad substrate scope was achieved in this modular water hydrogen gas as clean byproducts. The ortho-mono- ortho-disubstitutions were readily controlled by N-heterocyclic carbene (NHC) ligands amount base.

Language: Английский

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Manganese‐Catalyzed Mono‐N‐Methylation of Aliphatic Primary Amines without the Requirement of External High‐Hydrogen Pressure

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(13)

Published: Feb. 1, 2024

Abstract The synthesis of mono‐ N ‐methylated aliphatic primary amines has traditionally been challenging, requiring noble metal catalysts and high‐pressure H 2 for achieving satisfactory yields selectivity. Herein, we developed an approach the selective coupling methanol amines, without hydrogen, using a manganese‐based catalyst. Remarkably, up to 98 % with broad substrate scope were achieved at low catalyst loadings. Notably, due weak base‐catalyzed alcoholysis formamide intermediates, our novel protocol not only obviates addition but also prevents side secondary ‐methylation, supported by control experiments density functional theory calculations.

Language: Английский

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Iron-Catalyzed Metal–Ligand Cooperative Approach toward Sustainable Synthesis of Azines and N-Acylhydrazones in Air

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(5), P. 2921 - 2934

Published: Jan. 31, 2022

Herein, we describe a metal-ligand cooperative approach for the sustainable synthesis of various aldazines, ketazines, and N-acylhydrazones via dehydrogenative functionalization alcohols with hydrazine hydrate using simple, easy-to-prepare iron catalyst featuring redox noninnocent tridentate arylazo backbone. Our is compatible both primary secondary to produce wide variety substituted in good isolated yields air. A series control experiments are performed elucidate reaction mechanism.

Language: Английский

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