Terminal C(sp ³ )–H borylation through intermolecular radical sampling

Science, Год журнала: 2024, Номер 383(6682), С. 537 - 544

Опубликована: Фев. 1, 2024

Hydrogen atom transfer (HAT) processes can overcome the strong bond dissociation energies (BDEs) of inert C(sp

Язык: Английский

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Photoelectrochemically driven iron-catalysed C(sp3)−H borylation of alkanes

Nature Synthesis, Год журнала: 2024, Номер 3(4), С. 537 - 544

Опубликована: Янв. 31, 2024

Язык: Английский

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Catalysis in the Excited State: Bringing Innate Transition Metal Photochemistry into Play

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4665 - 4680

Опубликована: Март 5, 2025

Transition metal catalysis is an indispensable tool for organic synthesis that has been harnessed, modulated, and perfected many decades by careful selection of centers ligands, giving rise to synthetic methods with unparalleled efficiency chemoselectivity. Recent developments have demonstrated how light irradiation can also be recruited as a powerful dramatically alter the outcome catalytic reactions, providing access innovative pathways remarkable potential. In this context, adoption photochemical conditions mainstream strategy drive reactions unveiled exciting opportunities exploit rich excited-state framework transition metals applications. This Perspective examines advances in application complexes standalone photocatalysts, exploiting innate reactivity their excited states beyond common use photoredox catalysts. An account relevant examples dissected provide discussion on electronic reorganization, orbitals involved, associated different types states. analysis aims practitioners fundamental principles guiding strategies understand, design, apply light-activation homogeneous synthesis.

Язык: Английский

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Photoelectrochemical oxidative C(sp3)−H borylation of unactivated hydrocarbons

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 16, 2023

Organoboron compounds are of high significance in organic synthesis due to the unique versatility boryl substituents access further modifications. The demand for incorporation moieties into molecular structures has witnessed significant progress, particularly C(sp3)-H borylation hydrocarbons. Taking advantage special characteristics photo/electrochemistry, we herein describe development an oxidative reaction under metal- and oxidant-free conditions, enabled by photoelectrochemical strategy. exhibits broad substrate scope (>57 examples), includes use simple alkanes, halides, silanes, ketones, esters nitriles as viable substrates. Notably, unconventional regioselectivity is achieved, with coupling site selectively located distal methyl group. Our method operationally easily scalable, offers a feasible approach one-step high-value organoboron building blocks from hydrocarbons, which would provide ample opportunities drug discovery.

Язык: Английский

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The great strides of iron photosensitizers for contemporary organic photoredox catalysis: On our way to the holy grail?

Coordination Chemistry Reviews, Год журнала: 2023, Номер 500, С. 215522 - 215522

Опубликована: Ноя. 9, 2023

Язык: Английский

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Visible-light induced direct C(sp³)–H functionalization: recent advances and future prospects

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(18), С. 5278 - 5305

Опубликована: Янв. 1, 2024

This review summarizes the latest methodological advances in photocatalytic C(sp 3 )–H functionalization, with a particular emphasis on formation of C–P, C–B, C–S bonds, etc ., and some prominent efforts asymmetric C–H functionalization.

Язык: Английский

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2-Aminophenanthroline Ligands Enable Mild, Undirected, Iridium-Catalyzed Borylation of Alkyl C–H Bonds

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(11), С. 7124 - 7129

Опубликована: Март 8, 2024

The catalytic, undirected borylation of alkyl C–H bonds typically occurs at high reaction temperatures or with excess substrate, both, because the low reactivity bonds. Here we report a new iridium system comprising 2-anilino-1,10-phenanthroline as ligand that catalyzes little to no induction period and rates. This superior activation profile 2-aminophenanthroline-ligated catalysts leads broader scope, including reactions sensitive substrates, such epoxides glycosidic acetals, enhanced diastereoselectivity, higher yields borylated products. These also enable alkanes, amines, ethers room temperature for first time. Mechanistic studies imply facile N-borylation under conditions complexes containing N-boryl aminophenanthrolines are competent precatalysts reaction.

Язык: Английский

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Iron-Catalyzed Ipso-Nitration of Aryl Borides via Visible-Light-Induced β-Homolysis

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 3306 - 3313

Опубликована: Фев. 7, 2025

Herein, we reported a practical method to realize ipso-nitration of boronic acids, their pinacol esters, and trifluoroborate salts with alkali metal salt NaNO3 as nitrating reagent. A FeIII/FeIV catalytic cycle involving an unusual visible-light-induced β-homolysis pathway the N–O bond in simple iron complex effectively provides nitryl radical key species. This protocol bears mild reaction conditions, broad scope (up 99% yield), good functional group compatibility, convenient scale-up synthesis.

Язык: Английский

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Visible-Light-Induced Excited-State Copper Catalysis: Recent Advances and Perspectives

ACS Catalysis, Год журнала: 2024, Номер 14(16), С. 11974 - 11989

Опубликована: Июль 26, 2024

Photoactive copper complexes have gained significant attention due to their photocatalytic activities. Different homogeneous Cu(I) complexes, Cu(II) and heterogeneous copper-based photocatalysts been investigated utilized in a broad spectrum of organic transformations. These applications span radical additions, C–C bond C–heteroatom cross-couplings, aerobic oxidative reactions, kinetic resolutions. This review summarizes the advancements this dynamic field visible-light-induced, excited-state copper-catalyzed reactions over recent years. It is organized according type excited species involved provides perspective on current future developments.

Язык: Английский

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Selective Arene Photonitration via Iron-Complex β-Homolysis

JACS Au, Год журнала: 2024, Номер 4(12), С. 4899 - 4909

Опубликована: Ноя. 21, 2024

Nitroaromatics, as an important member and source of nitrogen-containing aromatics, is bringing enormous economic benefits in fields pharmaceuticals, dyes, pesticides, functional materials, fertilizers, explosives. Nonetheless, the notoriously polluting nitration industry, which suffers from excessive discharge fumes waste acids, poor group tolerance, tremendous purification difficulty, renders mild, efficient, environmentally friendly a formidable challenge. Herein, we develop visible-light-driven biocompatible arene C–H strategy with good efficiency regioselectivity, marvelous substrate applicability wide application scale-up synthesis, total late-stage functionalization. A nitryl radical delivered through unusual β-homolysis photoexcited ferric-nitrate complex proposed to be key nitrification reagent this system.

Язык: Английский

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