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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Commercial Pd/C-Catalyzed N-Methylation of Nitroarenes and Amines Using Methanol as Both C1 and H₂ Source

The Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 84(23), P. 15389 - 15398

Published: Nov. 8, 2019

Herein, we report commercially available carbon-supported-palladium (Pd/C)-catalyzed N-methylation of nitroarenes and amines using MeOH as both a C1 H2 source. This transformation proceeds with high atom-economy in an environmentally friendly way via borrowing hydrogen mechanism. A total >30 structurally diverse N-methylamines, including bioactive compounds, were selectively synthesized isolated yields up to 95%. Furthermore, selective deuteration nimesulide, nonsteroidal anti-inflammatory drug, realized through the late-stage functionalization.

Language: Английский

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The Deuterated “Magic Methyl” Group: A Guide to Site‐Selective Trideuteromethyl Incorporation and Labeling by Using CD₃Reagents

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(46), P. 11751 - 11772

Published: June 2, 2021

Abstract In the field of medicinal chemistry, precise installation a trideuteromethyl group is gaining ever‐increasing attention. Site‐selective incorporation deuterated “magic methyl” can provide profound pharmacological benefits and be considered an important tool for drug optimization development. This review provides structured overview, according to trideuteromethylation reagent, currently established methods site‐selective carbon atoms. addition CD 3 , selective introduction 2 H CDH groups also considered. For all methods, corresponding mechanism scope are discussed whenever reported. As such, this starting point synthetic chemists further advance methodologies. At same time, aims guide chemists, offering them available C−CD formation strategies preparation new or modified drugs.

Language: Английский

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

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(22), P. 15013 - 15053

Published: Nov. 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.

Language: Английский

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B(C₆F₅)₃-Catalyzed Direct C3 Alkylation of Indoles and Oxindoles

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(8), P. 4835 - 4840

Published: April 9, 2020

The direct C3 alkylation of indoles and oxindoles is a challenging transformation, only few methods exist. Utilizing the underexplored ability triaryl boranes to mediate heterolytic cleavage α-nitrogen C-H bonds in amines, we have developed catalytic approach for wide range using amine-based alkylating agents. We also employed this borane-catalyzed strategy an alkylation-ring opening cascade.

Language: Английский

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N-Methylation of Amines with Methanol in the Presence of Carbonate Salt Catalyzed by a Metal–Ligand Bifunctional Ruthenium Catalyst [(p-cymene)Ru(2,2′-bpyO)(H₂O)]

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(3), P. 2621 - 2631

Published: Jan. 27, 2021

A ruthenium complex [(p-cymene)Ru(2,2′-bpyO)(H2O)] was found to be a general and efficient catalyst for the N-methylation of amines with methanol in presence carbonate salt. Moreover, series sensitive substituents, such as nitro, ester, cyano, vinyl groups, were tolerated under present conditions. It confirmed that OH units ligand are crucial catalytic activity. Notably, this research exhibited potential metal–ligand bifunctional catalysts hydrogen autotransfer process.

Language: Английский

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Recent advances in sustainable organic transformations using methanol: expanding the scope of hydrogen-borrowing catalysis

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(24), P. 7077 - 7096

Published: Jan. 1, 2021

Recent progress relating to sustainable approaches using methanol as a C1-alkylating agent for C–Me and N–Me bond formation is discussed.

Language: Английский

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Well-Defined Bis(NHC)Mn(I) Complex Catalyzed Tandem Transformation of α,β-Unsaturated Ketones to α-Methylated Ketones Using Methanol

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(19), P. 12444 - 12457

Published: Sept. 28, 2022

Tandem transformation of α,β-unsaturated ketones to α-methylated by utilizing methanol as both the hydrogen and C1 sources is reported in presence a phosphine-free bis-N-heterocyclic carbene-Mn(I) (bis-NHC-Mn(I)) catalyst. The dehydrogenative coupling between produces corresponding along with 1 equiv formaldehyde water. Among different bis-NHC-Mn(I) complexes, ethyl wingtip-substituted complex triflate counteranion showed highest catalytic activity. This system was highly effective for reductive methylation wide variety substrates including aromatic, heteroaromatic, aliphatic straight chains containing ketones. Notably, this methodology led synthesis pharmaceutically important drug molecules such eperisone lanperisone. Several control experiments, kinetic studies, Hammett density functional theory (DFT) calculations were carried out understand tandem process.

Language: Английский

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Recent advances in the catalytic N-methylation and N-trideuteromethylation reactions using methanol and deuterated methanol

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 474, P. 214827 - 214827

Published: Oct. 11, 2022

Language: Английский

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From hydrogen autotransfer process to deuterium autotransfer process: The N-trideuteromethylation of amines with deuterated methanol to trideuteromethylated amines catalyzed by a Cp*Ir complex bearing a flexible bridging and functional ligand

Journal of Catalysis, Journal Year: 2022, Volume and Issue: 410, P. 333 - 338

Published: April 25, 2022

Language: Английский

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