Borrowing Hydrogen for Organic Synthesis

ACS Central Science, Год журнала: 2021, Номер 7(4), С. 570 - 585

Опубликована: Март 25, 2021

Borrowing hydrogen is a process that used to diversify the synthetic utility of commodity alcohols. A catalyst first oxidizes an alcohol by removing form reactive carbonyl compound. This intermediate can undergo diverse range subsequent transformations before returns "borrowed" liberate product and regenerate catalyst. In this way, alcohols may be as alkylating agents whereby sole byproduct one-pot reaction water. recent decades, significant advances have been made in area, demonstrating many effective methods access valuable products. outlook highlights diversity metal biocatalysts are available for approach, well various performed, focusing on selection most advances. By succinctly describing conveying versatility borrowing chemistry, we anticipate its uptake will increase across wider scientific audience, expanding opportunities further development.

Язык: Английский

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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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Control of Absolute Stereochemistry in Transition‐Metal‐Catalysed Hydrogen‐Borrowing Reactions

Chemistry - A European Journal, Год журнала: 2020, Номер 26(57), С. 12912 - 12926

Опубликована: Апрель 16, 2020

Abstract Hydrogen‐borrowing catalysis represents a powerful method for the alkylation of amine or enolate nucleophiles with non‐activated alcohols. This approach relies upon catalyst that can mediate strategic series redox events, enabling formation C−C and C−N bonds producing water as sole by‐product. In majority cases these reactions have been employed to target achiral racemic products. contrast, focus this Minireview is hydrogen‐borrowing‐catalysed in which absolute stereochemical outcome process be controlled. Asymmetric hydrogen‐borrowing rapidly emerging synthesis enantioenriched carbonyl containing products examples involving both bond are presented. A variety different approaches discussed including use chiral auxiliaries, asymmetric enantiospecific processes.

Язык: Английский

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Chromium‐Catalyzed Alkylation of Amines by Alcohols

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(29), С. 11789 - 11793

Опубликована: Март 18, 2020

Abstract The alkylation of amines by alcohols is a broadly applicable, sustainable, and selective method for the synthesis alkyl amines, which are important bulk fine chemicals, pharmaceuticals, agrochemicals. We show that Cr complexes can catalyze this C−N bond formation reaction. synthesized isolated 35 examples alkylated including 13 previously undisclosed products, use amino as alkylating agents was demonstrated. catalyst tolerates numerous functional groups, hydrogenation‐sensitive examples. Compared to many other alcohol‐based amine methods, where stoichiometric amount base required, our Cr‐based system gives yields higher than 90 % various with catalytic base. Our study indicates borrowing hydrogen or autotransfer reactions could thus be an alternative Fe, Co, Mn, noble metals in (de)hydrogenation catalysis.

Язык: Английский

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Cobalt-catalyzed dehydrogenative functionalization of alcohols: Progress and future prospect

Coordination Chemistry Reviews, Год журнала: 2021, Номер 451, С. 214257 - 214257

Опубликована: Окт. 28, 2021

Язык: Английский

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Iron-Catalyzed α-Alkylation of Ketones with Secondary Alcohols: Access to β-Disubstituted Carbonyl Compounds

Organic Letters, Год журнала: 2020, Номер 22(5), С. 2064 - 2069

Опубликована: Фев. 24, 2020

An iron-catalyzed borrowing hydrogen strategy has been applied in the synthesis of β-branched carbonyl compounds. Various secondary benzylic and aliphatic alcohols have used as alkylating reagents under mild reaction conditions. The ketones isolated good to excellent yield. Deuterium labeling experiments provide evidence that alcohol is hydride source this no reversible step or hydrogen/deuterium scrambling takes place during process.

Язык: Английский

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Selective Catalytic Synthesis of α-Alkylated Ketones and β-Disubstituted Ketones via Acceptorless Dehydrogenative Cross-Coupling of Alcohols

Organic Letters, Год журнала: 2021, Номер 23(3), С. 869 - 875

Опубликована: Янв. 21, 2021

Herein, a phosphine-free pincer ruthenium(III) catalyzed β-alkylation of secondary alcohols with primary to α-alkylated ketones and two different β-branched are reported. Notably, this transformation is environmentally benign atom efficient H2O H2 gas as the only byproducts. The protocol extended gram-scale reaction for functionalization complex vitamin E cholesterol derivatives.

Язык: Английский

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Divergent Synthesis of Alcohols and Ketones via Cross‐Coupling of Secondary Alcohols under Manganese Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(26)

Опубликована: Апрель 21, 2023

A homogeneous manganese-catalyzed cross-coupling of two secondary alcohols for the divergent synthesis γ-disubstituted and β-disubstituted ketones is reported. Employing well-defined Mn-MACHOPh as catalyst, this novel protocol has a broad substrate scope with good functional group tolerance affords diverse library valuable disubstituted in moderate to yields. The strong influence reaction temperature on selective formation alcohol products was theorized preliminary DFT studies. Studies have shown that Gibbs free energy thermodynamically more favourable than corresponding at lower temperature.

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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Manganese complex-catalysed α-alkylation of ketones with secondary alcohols enables the synthesis of β-branched carbonyl compounds

Chemical Communications, Год журнала: 2020, Номер 56(60), С. 8376 - 8379

Опубликована: Янв. 1, 2020

Herein, β-branched carbonyl compounds were synthesised via the α-alkylation of ketones with secondary alcohols under "borrowing hydrogen" catalysis. A wide range alcohols, including various cyclic, acyclic, symmetrical, and unsymmetrical have been successfully applied developed reaction conditions. manganese(i) complex bearing a phosphine-free multifunctional ligand catalysed produced water as sole byproduct.

Язык: Английский

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