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

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4607 - 4647

Published: Jan. 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.

Language: Английский

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Progressive study on ruthenium catalysis for de(hydrogenative) alkylation and alkenylation using alcohols as a sustainable source

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(41), P. 7998 - 8030

Published: Jan. 1, 2022

This review focuses on the Ru-catalyzed de(hydrogenative) formation of C–C and CC bonds. The comparative reactivity different Ru-complexes to gain selectivity in product is presented, together with brief mechanistic insights.

Language: Английский

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Recent advances in C/N-alkylation with alcohols through hydride transfer strategies

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(39), P. 7713 - 7745

Published: Jan. 1, 2022

Recent advances in C/N alkylation using alcohols as alkylating reagents via hydrogen-shuttle methodologies: Borrowing Hydrogen, Acceptorless Dehydrogenative Coupling, and Base-mediated Hydride Transfer.

Language: Английский

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Manganese-catalyzed cyclopropanation of allylic alcohols with sulfones

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 9, 2024

Cyclopropanes are among the most important structural units in natural products, pharmaceuticals, and agrochemicals. Herein, we report a manganese-catalyzed cyclopropanation of allylic alcohols with sulfones as carbene alternative precursors via borrowing hydrogen strategy under mild conditions. Various arylmethyl trifluoromethyl work efficiently this transformation thereby deliver corresponding cyclopropylmethanol products 58% to 99% yields. Importantly, major benefit is that versatile free alcohol moiety retained resultant which can undergo wide range downstream transformations provide access series functional molecules. Mechanistic studies support sequential reaction mechanism involves catalytic dehydrogenation, Michael addition, cyclization, hydrogenation.

Language: Английский

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Recent Developments of Transition‐Metal‐Catalyzed Cross‐Coupling of Nitriles and Alcohols

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(32)

Published: Aug. 22, 2024

Abstract Cross‐coupling of nitriles and alcohols offers an environmentally friendly atom‐economical method for the synthesis various valuable compounds. These compounds include α ‐alkylated ‐olefinated nitriles, primary amines, imines, N ‐alkylation amides, ‐heterocycles, δ ‐hydroxynitriles, olefins, etc . Herein, we have reviewed recent developments (from 2013–date) transition‐metal‐catalyzed cross‐coupling alcohols. A number transition metal complexes such as noble metals Ru Ir, well base Mn, Fe, Co, Ni are presented. Moreover, different product types, reaction conditions mechanisms discussed to understand catalyst development.

Language: Английский

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Ruthenium‐Catalyzed α‐Alkylation of Arylacetonitriles with Primary Alcohols: N‐heterocyclic Carbene‐Amine's Promotional Influence

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(7)

Published: Feb. 1, 2025

Abstract Transition‐metal‐catalyzed α‐alkylation of nitriles with alcohols is an environmentally benign reaction, and the development simple efficient catalysts for this transformation a growing area research. In study, we report serial bidentate N ‐heterocyclic carbene (NHC) ruthenium complexes different extra donors alcohols. Through adjusting backbone NHC ligands, catalytic activities these could be controlled. The complex ( Ru3 ) bearing amine donor benzimidazolium exhibited highest activity. A large variety α‐alkylated were obtained in 30%–88% yields, by using 1 mol% amount Cs 2 CO 3 (20 mol%). Detailed control experiments deuterium‐labeling suggested that reaction proceeds via borrowing hydrogen pathway.

Language: Английский

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Manganese catalyzed cross-coupling of allylic alcohols and nitriles: an elegant route for access to δ-hydroxynitriles

Green Chemistry, Journal Year: 2022, Volume and Issue: 25(1), P. 357 - 364

Published: Nov. 30, 2022

A first example of a manganese pincer complex for synthesis δ-hydroxynitriles through formal conjugate addition nitriles with allylic alcohols 100% atom economy.

Language: Английский

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Chemoselective α‐Alkylation of Nitriles with Primary Alcohols by Manganese(I)‐Catalysis

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(13)

Published: May 8, 2023

A sustainable and easy-to-use protocol for the alkylation of aryl nitriles with earth-abundant manganese(I) catalyst is presented. The reaction employs readily available naturally abundant alcohols as coupling partners. proceeds chemoselectively encompasses a broad substrate scope good to excellent yields. catalytic yields selectively α-branched water sole byproduct. Experimental studies were executed understand mechanism reaction.

Language: Английский

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Ruthenium‐Catalyzed Selective α‐Alkylation of β‐Naphthols using Primary Alcohols: Elucidating the Influence of Base and Water

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(59)

Published: July 24, 2023

Abstract Functionalized arenes and arenols have diverse applications in chemical synthesis material chemistry. Selective functionalization of is a topic prime interest. In particular, direct alkylation using alcohols challenging task. this report, ruthenium pincer catalyzed α‐alkylation β‐naphthol primary as alkylating reagents reported. Notably, aryl heteroaryl methanols linear branched aliphatic underwent selective reactions, which water the only byproduct. catalytically derived α‐alkyl‐β‐naphthol products displayed high absorbance, emissive properties, quantum yields (up to 93.2 %). Dearomative bromination on demonstrated synthetic application. Mechanistic studies indicate that reaction involves an aldehyde intermediate. DFT support finding further reveal stoichiometric amount base required make aldol condensation well elementary steps for regeneration active species. situ‐generated molecule from plays important role catalyst.

Language: Английский

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