Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4237 - 4352

Опубликована: Янв. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Язык: Английский

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Practical and General Alcohol Deoxygenation Protocol

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(18)

Опубликована: Фев. 25, 2023

Herein, we describe a practical protocol for the removal of alcohol functional groups through reductive cleavage their benzoate ester analogs. This transformation requires strong single electron transfer (SET) reductant and means to accelerate slow fragmentation following substrate reduction. To accomplish this, developed photocatalytic system that generates potent from formate salts alongside Brønsted or Lewis acids promote reduced intermediate. deoxygenation procedure is effective across structurally electronically diverse alcohols enables variety difficult net transformations. no precautions exclude air moisture remains efficient on multigram scale. Finally, can be adapted one-pot benzoylation-deoxygenation sequence enable direct deletion. Mechanistic studies validate role acidic additives key C(sp

Язык: Английский

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Visible-Light-Driven Photocatalyst-Free Deoxygenative Radical Transformation of Alcohols to Oxime Ethers

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(6), С. 3975 - 3980

Опубликована: Фев. 27, 2023

A visible-light-driven deoxygenative cross-coupling of alcohols with sulfonyl oxime ethers has been developed by using xanthate salts as alcohol-activating groups. Upon convenient generation and direct photoexcitation anions, a broad range including primary ones can efficiently undergo this transformation to afford diverse derivatives. This one-pot protocol features mild conditions, substrate scope, late-stage applicability, without the need for any external photocatalysts or electron donor-acceptor complex formation.

Язык: Английский

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Asymmetric synthesis of unnatural α-amino acids through photoredox-mediated C–O bond activation of aliphatic alcohols

Chemical Science, Год журнала: 2024, Номер 15(19), С. 7316 - 7323

Опубликована: Янв. 1, 2024

A practical protocol for the stereoselective synthesis of unnatural α-amino acids is disclosed, using ubiquitous aliphatic alcohols as radical precursors to form acid backbone under redox-neutral photoredox-mediated conditions.

Язык: Английский

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SuFEx-Enabled Direct Deoxy-Diversification of Alcohols

Organic Letters, Год журнала: 2024, Номер 26(18), С. 4013 - 4017

Опубликована: Май 1, 2024

We introduce a new use of sulfonyl fluoride as bifunctional reagent that facilitates the one-step deoxy-diversification complex alcohol libraries. Our reaction design features Sulfur(VI) Fluoride Exchange (SuFEx) mediated activation alcohols and fluoride-induced silicon-bound nucleophiles. This method enables direct conversion alcoholic C–O bonds in molecules into diverse analogues via C–C, C–N, C–Cl, C–Br bond formation while suppressing any elimination side-products.

Язык: Английский

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Modular alkene synthesis from carboxylic acids, alcohols and alkanes via integrated photocatalysis

Nature Chemistry, Год журнала: 2024, Номер 16(11), С. 1822 - 1830

Опубликована: Сен. 27, 2024

Язык: Английский

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Visible-light-driven photocatalyst-free deoxygenative alkylation of imines with alcohols

Chemical Communications, Год журнала: 2022, Номер 58(92), С. 12843 - 12846

Опубликована: Янв. 1, 2022

In this report, we developed a photocatalyst-free visible-light-promoted deoxygenative alkylation of imines with alcohols assisted by carbon disulfide and tricyclohexylphosphine. The key to success method is the activation upon formation direct photoexcitation xanthate anions. This one-pot protocol enables selective C-O bond homolysis diverse primary, secondary tertiary react variety N-sulfonyl N-aryl imines, providing general efficient platform for α-branched amine synthesis from alcohols.

Язык: Английский

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Divergent Synthesis of Organofluorinated Molecules from Titanium Mediated Deoxygenation of Free Alcohols

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(15), С. 1783 - 1790

Опубликована: Апрель 10, 2023

Comprehensive Summary Alcohols as among the most widely occurring organic compounds known, deoxygenative transformations of free alcohols partners in radical addition reactions remain formidable challenges with great opportunities to achieve new and useful transformations. Herein, we report a protocol via C—O bond cleavage C—C bond‐forming reaction trifluoromethyl alkenes assisted by titanium reagents strategy, enabling divergent synthesis for functional‐group‐rich organofluorinated high efficiencies. In this transformation, tertiary Ti‐catalysis could be converted alkanes without defluorination acidic conditions, while benzyl are employed Ti‐mediated activation supply gem ‐difluoroalkenes presence base. This is applicable broad range good functional group tolerance variety (including primary, secondary, alcohols), scalable gram level. Remarkably, utility demonstrated several derivatizations late‐stage functionalization drug molecules. The successful applications scale up molecules demonstrate its potential synthetic value discovery settings.

Язык: Английский

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Visible-Light-Driven Deoxygenative Heteroarylation of Alcohols with Heteroaryl Sulfones

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(5), С. 3629 - 3634

Опубликована: Фев. 16, 2024

The visible-light-promoted deoxygenative radical heteroarylation of alcohols was achieved in the absence any external photosensitizers. processes occur through generation xanthate salts from alcohols, followed by SET and fragmentation, delivering alkyl radicals to react with heteroaryl sulfones. This method is amenable for a wide range good functional group tolerance, providing practical strategy alkylation benzo-heteroaromatics. Mechanism studies indicate that direct visible-light excitation anions subsequent initiate reactions.

Язык: Английский

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Demystifying the recent photochemical and electrochemical tricks on installing the magic methyl group: A comprehensive overview

Green Chemistry, Год журнала: 2024, Номер 26(14), С. 8161 - 8203

Опубликована: Янв. 1, 2024

The strategic installation of the “magic methyl” group has become highly desirable for drug discovery. This review summarized recent photochemical and electrochemical strategies in installing methyl group.

Язык: Английский

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