Dinuclear gold-catalyzed divergent dechlorinative radical borylation of gem-dichloroalkanes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 2, 2024

The enormous and widespread use of organoboronic acids has prompted the development innovative synthetic methodologies to meet demands on structural diversity functional group tolerance. existing photoinduced defunctionalization radical borylation, typically focused conversion one C-X bond (X= Br, I, or other leaving group) into only C-B bond. Herein, we disclose a divergent dechloroborylation reaction enabled by dinuclear gold catalysis with visible light irradiation. A wide range structurally diverse alkyl boronic, α-chloroboronic, gem-diboronic esters can be synthesized in moderate good yields (up 92%). Its robustness is further demonstrated preparative scale applied late-stage diversification complex molecules. process hinges C-Cl relay activation readily available gem-dichloroalkanes through inner-sphere electron transfer, overcoming redox potential limits unreactive chlorides.

Язык: Английский

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Energy-transfer-enabled photocatalytic transformations of aryl thianthrenium salts

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 8, 2024

Aryl thianthrenium salts are valuable in photocatalysis but traditionally require external electron donors for activation. This study introduces an energy transfer (EnT) strategy the activation of aryl using 2,3,4,5,6-penta(carbazol-9-yl)benzonitrile (5CzBN) as a metal-free photocatalyst, eliminating need donors. Utilizing this EnT approach, we achieve C-H deuteration arenes under visible light with CDCl

Язык: Английский

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Potassium-modified carbon nitride photocatalyzed-aminoacylation of N‑sulfonyl ketimines

Chinese Chemical Letters, Год журнала: 2024, Номер 36(2), С. 110250 - 110250

Опубликована: Июль 17, 2024

Язык: Английский

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Photocatalytic organosulfur reagent-promoted selective mono-(deutero)hydrodechlorination

Green Chemistry, Год журнала: 2024, Номер 26(9), С. 5167 - 5172

Опубликована: Янв. 1, 2024

Selective partial C–Cl bond reduction represents an important strategy for the construction of valuable chlorine-containing skeletons.

Язык: Английский

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Programmable synthesis of difluorinated hydrocarbons from alkenes through a photocatalytic linchpin strategy

Chemical Science, Год журнала: 2023, Номер 14(41), С. 11546 - 11553

Опубликована: Янв. 1, 2023

The introduction of difluoromethylene moieties into organic molecules has garnered significant attention due to their profound influence on the physicochemical and biological properties compounds. Nonetheless, existing approaches for accessing difluoroalkanes from readily available feedstock chemicals remain limited. In this study, we present an efficient modular protocol synthesis difluorinated compounds alkenes, employing accessible reagent, ClCF2SO2Na, as a versatile "difluoromethylene" linchpin. By means organophotoredox-catalysed hydrochlorodifluoromethylation followed by ligated boryl radical-facilitated halogen atom transfer (XAT) process, have successfully obtained various compounds, including gem-difluoroalkanes, gem-difluoroalkenes, difluoromethyl alkanes, with satisfactory yields. practical utility linchpin strategy been demonstrated through successful preparation CF2-linked derivatives complex drugs natural products. This method opens up new avenues structurally diverse hydrocarbons highlights radicals in organofluorine chemistry.

Язык: Английский

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Cobalt-catalyzed cross-electrophile coupling of alkynyl sulfides with unactivated chlorosilanes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 27, 2024

Abstract Herein, we disclose a highly efficient cobalt-catalyzed cross-electrophile alkynylation of broad range unactivated chlorosilanes with alkynyl sulfides as stable and practical electrophiles. Strategically, employing easily synthesized precursors allows access to various alkynylsilanes in good excellent yields. Notably, this method avoids the utilization strong bases, noble metal catalysts, high temperature forcing reaction conditions, thus presenting apparent advantages, such substrate scope (72 examples, up 97% yield), Csp-S chemo-selectivity functional group compatibility (Ar-X, X = Cl, Br, I, OTf, OTs). Moreover, utilities are also illustrated by downstream transformations late-stage modification structurally complex natural products pharmaceuticals. Mechanistic studies elucidated that cobalt catalyst initially reacted sulfides, activation occurred via an S N 2 process instead radical pathway.

Язык: Английский

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Recent progress in visible light‐driven halogenation: Chlorination, bromination, and iodination

Bulletin of the Korean Chemical Society, Год журнала: 2024, Номер 45(9), С. 738 - 758

Опубликована: Сен. 1, 2024

Abstract Halogenation is one of the most important transformations in organic synthesis. Halogenated compounds are employed many reactions to prepare useful molecules. Many methods have been developed introduce halogens into different compounds. Visible light‐mediated efficient, low‐toxic, and mild‐condition applied for various chemistry transformations. Remarkably, there has an increasing development application visible light‐induced halogenation recent years. Herein, we present a comprehensive summary including chlorination, bromination, iodination under light irradiation since 2020.

Язык: Английский

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Photoinduced N-heterocyclic nitrenium-catalyzed single electron reduction of Se–Se bond for the generation of nucleophilic selenolates

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(7), С. 2070 - 2074

Опубликована: Янв. 1, 2024

A straightforward photoinduced NHN-catalyzed method for generating nucleophilic selenolates from diselenides without the need of stoichiometric reductants.

Язык: Английский

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Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp³)–C(sp³) Bond Formation

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 12, 2024

The ligated boryl radical (LBR) has emerged as a potent tool for activating alkyl halides in transformations through halogen-atom transfer (XAT). However, unactivated chlorides still present an open challenge this strategy. We herein describe new activation mode of the LBR to construct C(sp

Язык: Английский

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Practical photocatalytic hydroalkylation of alkenes with chloroacetates mediated by the formate ion

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(10), С. 2829 - 2833

Опубликована: Янв. 1, 2024

Commodity chemicals are used as alkylating and reducing agents for radical addition to alkenes. The method is based on activation of the strong C–Cl bond by anion carbon dioxide.

Язык: Английский

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