Merging Photoinduced Electron Transfer with Hydrogen Atom Transfer: Formal β-C(sp³)–H Pyridination of Carbonyls

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 9, 2025

In this study, a novel approach that combines photoinduced electron transfer (ET) with hydrogen atom (HAT) has been introduced for the selective β-C(sp3)–H pyridination of carbonyl compounds. This method is notable its absence transition metals and ability to function under benign reaction conditions, resulting in range pyridinated derivatives consistently moderate good yields. The significance technique further underscored by potential late-stage functionalization pharmaceutically significant molecules. Mechanistic investigations confirmed proceeds via radical-mediated pathway.

Язык: Английский

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Electroreduction strategy: a sustainable tool for the generation of aryl radicals

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(15), С. 4318 - 4342

Опубликована: Янв. 1, 2024

This review primarily focuses on the generation of aryl radicals via an electroreduction strategy, and systematically elaborates synthetic applications, scope, limitations substrates.

Язык: Английский

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The Strategies towards Electrochemical Generation of Aryl Radicals

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Июль 16, 2024

The advancement in electrochemical techniques has unlocked a new path for achieving unprecedented oxidations and reductions of aryl radical precursors controlled selective manner. This approach facilitates the construction aromatic carbon-carbon carbon-heteroatom bonds. In light green merits growing importance this technique chemistry, review aims to provide an overview recent advance generation radicals organized by precursor type, with focus on substrate scope, limitation, underlying mechanism, thereby inspiring future work generation.

Язык: Английский

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Photoredox Site-Selective C(sp³)–H Alkylation of 1-(o-Iodoaryl)-alkan-1-ones with Activated Alkenes Enabled by Hydrogen Atom Transfer

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 13, 2025

A visible-light-mediated photoredox catalysis for β-C(sp3)–H alkylation of 1-(o-iodoaryl)alkan-1-ones with alkenes via 1,5-hydrogen atom transfer and alkene alkylarylation to produce diverse β-alkyl arylalkanones containing a quaternary carbon center is presented. This method applicable wide range activated alkenes. Mechanistic studies suggest that the reaction involves radical process.

Язык: Английский

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Organo-mediator enabled electrochemical transformations

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review highlights organo-mediators that enable electrochemical reactions via outer-sphere electron transfer (ET), offering advantages such as availability, tunability, and simplified post-processing compared to direct electrolysis.

Язык: Английский

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Electroreductive Cross-Coupling Reactions: Carboxylation, Deuteration, and Alkylation

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Дек. 13, 2024

ConspectusElectrochemistry has been used as a tool to drive chemical reactions for more than two centuries. With the help of an electrode and power source, chemists are provided with system whose potential can be precisely dialed in. The theoretically infinite redox range renders electrochemistry capable oxidizing or reducing some most tenacious compounds. Indeed, electroreduction offers alternative generating highly active intermediates from electrophiles (e.g., halides, alkenes, etc.) in organic synthesis, which untouchable traditional reduction methods. Meanwhile, reductive coupling extensively utilized both industrial academic settings due their ability swiftly, accurately, effectively construct C–C C–X bonds, present innovative approaches synthesizing complex molecules. Nonetheless, its application is constrained by several inherent limitations: (a) requirement stoichiometric quantities agents, (b) scarce activation strategies inert substrates high potentials, (c) incomplete mechanistic elucidation, (d) challenges isolation intermediates. merging represents attractive approach address above limitations synthesis seen increasing use synthetic community over past few years.Since 2020, our group dedicated developing electroreductive cross-coupling using readily available small molecules, such arenes, CO2, D2O, value-added products. Electroreductive chemistry versatile powerful capacity precise selectivity control, allowed us develop three electrochemical modes lab: (1) An economically advantageous direct (EDR) strategy that emphasizes efficiency, achieves atom utilization, minimizes unnecessary atomic waste. (2) A class organo-mediated (EOMR) methods controlling reaction pathways. This allows modulation processes enhance efficiency selectivity. (3) metal-catalyzed (EMCR) method enables selective functionalization specific bonds functional groups under mild conditions, thereby occurrence side reactions. We commenced studies establishing organic-mediator-promoted carboxylation aryl alkyl halides. was then employed arylcarboxylation simple styrenes halides manner. electrolysis arenes epoxides CO2 carboxyl source achieved. Moreover, through adjustment we successfully accomplished deuteration olefins, unactivated enabling efficient formation D-labeled Finally, building on previous understanding developed series alkylation enable C(sp3)–C(sp3)

Язык: Английский

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Aryl-to-alkyl radical relay arylation reaction of remote C(sp3)-H bond using 1,4-dicyanobenzene as an electrochemical redox-mediator

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(15), С. 4182 - 4186

Опубликована: Янв. 1, 2024

In this paper, we developed an electro-reductive aryl-to-alkyl radical relay arylation reaction of a remote C(sp 3 )–H bond via 1,5-HAT process. This protocol features mild conditions, simple operation, and broad substrate scope.

Язык: Английский

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Divergent Synthesis of (E)- and (Z)-Alkenones via Photoredox C(sp³)–H Alkenylation–Dehydrogenation of o-Iodoarylalkanols with Alkynes

Organic Letters, Год журнала: 2024, Номер 26(47), С. 10096 - 10101

Опубликована: Ноя. 15, 2024

A photoredox C(sp3)–H alkenylation–dehydrogenation of o-iodoarylalkanols with terminal alkynes for the synthesis (E)- and (Z)-quaternary carbon center-containing pent-4-en-1-ones is described. The stereoselectivity depends on utilization photocatalysts. While using an organic photocatalyst like 4-DPAIPN manipulates arylalkynes to assemble (E)-pent-4-en-1-ones, in case Ir potocatalyst such as Ir(ppy)2(dtbbpy)PF6 reaction delivers (Z)-pent-4-en-1-ones. For alkylalkynes, furnishes (E)-pent-4-en-1-ones exclusively presence or Ir(ppy)2(dtbbpy)PF6.

Язык: Английский

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Photoreductive 1,4-Dicarbofunctionalization of 1,3-Enynes with Organoiodides and Cyanoarenes via Halogen-Atom Transfer

Organic Letters, Год журнала: 2024, Номер 26(36), С. 7661 - 7666

Опубликована: Авг. 28, 2024

A photoreductive halogen-atom transfer (XAT) strategy for 1,4-dicarbofunctionalization of 1,3-enynes with organoiodides and cyanoarenes is disclosed, enabling access to functionalized allenes in a highly regio-, chemo-, stereoselective manner. Upon the photoredox catalysis activation Et

Язык: Английский

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Dearomative Cyclization/Spirocyclization via Electrochemical Reductive Hydroarylation of Nonactivated Arenes

Organic Letters, Год журнала: 2024, Номер 26(42), С. 8993 - 8998

Опубликована: Окт. 14, 2024

An electrochemical cyclization/spirocyclization hydroarylation via reductive dearomatization of a series nonactivated arenes including

Язык: Английский

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