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

Chemical Reviews, Год журнала: 2024, Номер 124(9), С. 6078 - 6144

Опубликована: Апрель 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

Язык: Английский

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Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds

Chemical Society Reviews, Год журнала: 2024, Номер 53(9), С. 4607 - 4647

Опубликована: Янв. 1, 2024

This review collectively discussed the utilisation of alcohols in various organic transformations and their application toward intermediates drugs, drug derivatives natural product-like molecules.

Язык: Английский

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Multi-Functionality of Methanol in Sustainable Catalysis: Beyond Methanol Economy

ACS Catalysis, Год журнала: 2023, Номер 13(22), С. 15013 - 15053

Опубликована: Ноя. 6, 2023

Methanol is a fundamental feedstock and widely used in the chemical petroleum industries. It can serve as C1 source to make variety of C–C C–N bond formation dehydrogenative coupling products, which have important applications natural products drug discovery. A high hydrogen content (12.5 wt%) methanol makes it an effective H2 donor for transfer hydrogenation various reducible functional groups. plethora transition metal-based processes been developed using methanol. Notably, recent review articles focused on aspect However, more updated that examines challenges both C1-source H2-source organic transformations contributing concept economy has not presented yet. This Review summarizes (homogeneous, heterogeneous, photo-) catalyst system C-, N-, O-methylation ketones, alcohols, amides, nitriles, heterocyclic compounds, sulfones, amines, sulfonamides direct N-methylation nitro compounds under borrowing strategy N-formylation amines acceptorless dehydrogenation source. also covers insights into reaction mechanisms role carefully selected ligands metal catalysis activation incorporation -CD3, methylation molecules. Moreover, describes groups such aldehydes, alkynes, with detail.

Язык: Английский

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Molybdenum disulfide-catalyzed direct α-hydroxymethylation of amides employing methanol as a sustainable C1 source under photoirradiation

Journal of Catalysis, Год журнала: 2023, Номер 427, С. 115100 - 115100

Опубликована: Авг. 22, 2023

Язык: Английский

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Recent advances on cross-coupling of alcohols via borrowing hydrogen catalysis

Chemical Communications, Год журнала: 2024, Номер 60(30), С. 4002 - 4014

Опубликована: Янв. 1, 2024

This article highlights the recent advances and significance of β-alkylation reactions towards synthesis higher order alcohols.

Язык: 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, Год журнала: 2024, Номер 63(13)

Опубликована: Фев. 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.

Язык: Английский

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Advances in the homogeneous catalyzed alcohols homologation: The mild side of the Guerbet reaction. A mini-review

Catalysis Today, Год журнала: 2023, Номер 423, С. 114003 - 114003

Опубликована: Янв. 20, 2023

The Guerbet reaction would be an optimal solution for bio-ethanol refinery by homologation and it substantially requires the development of active highly selective catalysts. Although heterogeneous catalysis remains more desirable, homogeneous catalytic systems are nowadays acknowledged as challenging proposals high selectivity conversion under mild conditions. Several molecular bi-functional catalysts, based on ruthenium, iridium manganese complexes bearing different ligands such phosphine, bidentate bisphosphine (P-P) phosphamine (P-N), pincer (N-N-N), (P-N-P) cyclopentadienone, in co-presence a base, which is essential all cases condensation reaction. This mini-review aimed to describe state art, with incremental steps forward understand role conditions selectivity. While showing efficiency, mutable behavior minimal change ligand scaffold, variation water tolerance only one example recyclability, metal catalysts found similar terms proposed mechanisms. influence additives capability maintain activity fermentation broth from wine value chain second generation bio-fuel also discussed. not yet completely rationalized, experimental theoretical mechanistic investigations pave way design stable efficient toward improved applicability.

Язык: Английский

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Direct Synthesis of Gem-β,β′-Bis(alkyl) Alcohols Using Nickel Catalysis via Sequential DCR Approach

ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 4018 - 4029

Опубликована: Фев. 28, 2024

Chemoselective synthesis of functionalized gem-β,β′-bis(alkyl)alcohols by coupling a β-alkylated secondary alcohol with primary is reported using nickel via sequential DCR (dehydrogenation–condensation–rehydrogenation) approach. Using our method, 1-arylethanol and benzyl alcohols undergo one-pot successive double alkylation reaction to form alcohols. Methanol, C2–C12 alcohols, citronellol, fatty acid-derived oleic are tolerated, including late-stage functionalization steroid hormones (cholesterol testosterone) 5-pregnen-3β-ol-20-one. The catalytic transformations enabled the donepezil drug (used for Alzheimer's disease), N-heteroarenes (quinoline acridine), chromane intermediate flavan derivatives. Hammett kinetic plot analysis differently p-substituted 1-phenyl propanol indicated that oxidation might be rate-determining step expected strong influence substitution on kinetics. A negative ρ value (−0.60) strongly signify formation positive charge alcohol. Preliminary mechanistic investigation revealed dehydrogenation aldehyde as it involves C–H/D bond breaking alcohol, PH/PD 6.0 was calculated. Reaction profile studies, EPR experiments, Hammett-plot cyclic voltammetry, UV–visible XPS analysis, structural electronic changes at Ni-center well behavior catalysts during progress reactions.

Язык: Английский

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General and selective homogeneous Ru-catalyzed transfer hydrogenation, deuteration, and methylation of functional compounds using methanol

Journal of Catalysis, Год журнала: 2023, Номер 425, С. 386 - 405

Опубликована: Июнь 28, 2023

Язык: Английский

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Recent advances in the selective semi-hydrogenation of alkyne to (E)-olefins

Chemical Communications, Год журнала: 2024, Номер 60(12), С. 1517 - 1533

Опубликована: Янв. 1, 2024

This article highlights the recent advances on newer technologies and important methodologies directed to ( E )-olefins from alkynes.

Язык: Английский

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