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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Photochemical Deoxygenative Hydroalkylation of Unactivated Alkenes Promoted by a Nucleophilic Organocatalyst

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(6)

Опубликована: Дек. 18, 2023

The direct utilization of simple and abundant feedstocks in carbon-carbon bond-forming reactions to embellish sp

Язык: Английский

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Selective Lactic Acid Synthesis via Ethylene Glycol Electrooxidation in Borate Buffer

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Efficient and selective electrochemical oxidation of biomass-derived ethylene glycol to lactic acid is achieved over nickel catalyst by controlling the pH electrolyte solution.

Язык: Английский

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Photocatalyzed Carbon─Carbon Bond Formation Between Ethylene Glycol and Electron‐Deficient Olefins

ChemistrySelect, Год журнала: 2025, Номер 10(1)

Опубликована: Янв. 1, 2025

Abstract Ethylene glycol is produced on a very large industrial scale and used for the preparation of polyesters antifreeze formulations. Although diol mainly manufactured from fossil‐based resources, new commercial procedures carbohydrates are currently being introduced, which eventually will make ethylene an important bio‐derived compound in organic chemistry. However, further transformations formation carbon─carbon bonds have so far received relatively little attention. In present work, photocatalyzed coupling between electron‐deficient olefins therefore investigated. The results show that iridium complex can be employed to mediate reaction with acrylates, acrylamides, acrylonitriles, vinyl sulfones generate range chain‐elongated lactones diols. Substituents tolerated α position acrylates while poor outcome obtained substituents β olefin. illustrate abundant alcohol by use photocatalytic transformations.

Язык: Английский

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Accelerated Screening of Covalent Organic Frameworks for Ethylene Glycol/1,2-Butanediol Separation by Interpretable Machine Learning

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 1823 - 1830

Опубликована: Фев. 13, 2025

The separation of ethylene glycol (EG) and 1,2-butanediol (1,2-BDO) azeotrope in the synthesis process EG via coal biomass is becoming increasingly commercial environmental importance. Selective adsorption deemed as most promising method because energy savings environment favorability. In this study, we developed an interpretable decision tree (DT) model to facilitate high-throughput screening covalent organic frameworks (COFs) adsorbents for EG/1,2-BDO mixtures, achieving R2 value 0.96. analysis has shown that using difference isosteric heat (ΔQst) between (Qst-EG) 1,2-BDO (Qst-BDO), combined with largest cavity diameter (LCD), effective selecting optimal COFs separation. ΔQst greater than 6.5 kcal/mol LCD ranging from 3.6 4.8 Å typically exhibit superior performance can serve preselection criteria accelerate process. Six high working capacity exceptional selectivity were selected selection principle. All containing strong electronegative groups. groups significantly amplify disparity strength 1,2-BDO, thereby boosting efficiency. principles proposed work be used guide design 1,2-BDO.

Язык: Английский

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Direct Synthesis of Polyesterether from Ethylene Glycol

ACS Sustainable Chemistry & Engineering, Год журнала: 2025, Номер unknown

Опубликована: Апрель 8, 2025

We report here a method for making polyesterether from ethylene glycol. The reaction is catalyzed by ruthenium complex and liberates H2 gas H2O as byproducts. Mechanistic studies conducted through experiments DFT computations suggest that the chain growth of polymerization process involves both dehydrogenation dehydration pathways stemming hemiacetal intermediate, leading to formation esters ethers, respectively. Investigations into other diols have also been conducted, showing with lower number carbons between alcohol groups (propylene glycol, glycerol, 1,3-propanediol) lead whereas α,ω-diols containing higher (1,6-hexanediol 1,10-decanediol) polyester.

Язык: Английский

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Heterogeneous catalytic dehydrogenative coupling of ethylene glycol and primary alcohols into α-hydroxycarboxylic acids

Science China Chemistry, Год журнала: 2023, Номер 66(9), С. 2583 - 2589

Опубликована: Авг. 8, 2023

Язык: Английский

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Manganese-catalyzed C–C and C–N bond formation with alcohols via borrowing hydrogen or hydrogen auto-transfer

Beilstein Journal of Organic Chemistry, Год журнала: 2024, Номер 20, С. 1111 - 1166

Опубликована: Май 21, 2024

Transition-metal-mediated "borrowing hydrogen" also known as hydrogen auto-transfer reactions allow the sustainable construction of C-C and C-N bonds using alcohols donors. In recent years, manganese complexes have been explored efficient catalysts in these reactions. This review highlights significant progress made manganese-catalyzed bond-formation via auto-transfer, emphasizing importance this methodology synthesis strategies.

Язык: Английский

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Divergent Synthesis of Pyrazoles via Manganese Pincer Complex Catalyzed Acceptorless Dehydrogenative Coupling Reactions

Chemistry - A European Journal, Год журнала: 2024, Номер 30(36)

Опубликована: Апрель 24, 2024

Abstract This report detailed the synthesis of multi‐substituted pyrazoles through acceptorless dehydrogenative coupling (ADC) reaction catalyzed by a well‐defined manganese(I)‐pincer complex. Symmetrically substituted were synthesized reacting 1,3‐diols with hydrazines. Unsymmetrically selectively made via ADC primary alcohols methyl hydrazones. Water and hydrogen are liberated as green byproducts. The endurance these methodologies has been presented producing 30 substrates varied functionalities. Model reactions scaled up to demonstrate practicability. rate order measured transparent involvement reagents during catalysis. Control experiments elucidated plausible mechanisms.

Язык: Английский

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Manganese catalyzed chemo-selective synthesis of acyl cyclopentenes: a combined experimental and computational investigation

Chemical Science, Год журнала: 2024, Номер 15(35), С. 14287 - 14294

Опубликована: Янв. 1, 2024

ADC/SET dual catalysis: manganese catalyzed acceptorless dehydrogenative coupling (ADC) and single electron transfer (SET) initiated vinyl cyclopropane ring expansion cascade enabled divergent synthesis of acyl cyclopentenes in high yields.

Язык: Английский

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