Organoelectrophotocatalytic C–H Silylation of Heteroarenes

Organic Letters, Год журнала: 2023, Номер 25(6), С. 1008 - 1013

Опубликована: Фев. 3, 2023

An organoelectrophotocatalytic approach for the C-H silylation of heteroarenes through dehydrogenation cross-coupling with H2 evolution has been developed. The strategy is carried out under a simple and efficient monocatalytic system by employing 9,10-phenanthrenequinone both as an organocatalyst hydrogen atom transfer (HAT) reagent, which avoids need external HAT oxidant, or metal reagent. A variety can be compatible in satisfactory yields excellent regioselectivity.

Язык: Английский

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Organophotoelectrochemical silylation cyclization for the synthesis of silylated 3-CF₃-2-oxindoles

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(14), С. 3585 - 3590

Опубликована: Янв. 1, 2023

An organophotoelectrochemical approach for silylation cyclization of CF3-substituted N -arylacrylamides with organosilanes under transition-metal-free and oxidant-free conditions has been developed.

Язык: Английский

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Recent advances in photo- and electro-enabled radical silylation

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(22), С. 6400 - 6415

Опубликована: Янв. 1, 2022

This review aims to highlight the recent advances in area of radical type silylation reactions mediated by photo- and electrocatalysis.

Язык: Английский

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Recent Advances in C–H Functionalisation through Indirect Hydrogen Atom Transfer

Molecules, Год журнала: 2023, Номер 28(16), С. 6127 - 6127

Опубликована: Авг. 18, 2023

The functionalisation of C–H bonds has been an enormous achievement in synthetic methodology, enabling new retrosynthetic disconnections and affording simple equivalents for synthons. Hydrogen atom transfer (HAT) is a key method forming alkyl radicals from substrates. Classic reactions, including the Barton nitrite ester reaction Hofmann–Löffler–Freytag reaction, among others, provided early examples HAT. However, recent developments photoredox catalysis electrochemistry have made HAT powerful tool capable introducing wide range functional groups into bonds. Moreover, greater mechanistic insights stimulated development increasingly site-selective protocols. Site-selectivity can be achieved through tuning electron density at certain using additives, judicious choice reagent, solvent system. Herein, we describe latest methods functionalizing C–H/Si–H/Ge–H indirect between 2018–2023, as well critical discussion reagents, aspects, substrate scopes, background contexts

Язык: Английский

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Decarboxylative Alkylation of Morita–Baylis–Hillman Acetates with Aliphatic Acids via Photochemical Iron-Mediated Ligand-to-Metal Charge Transfer

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

Опубликована: Фев. 28, 2025

Carboxylic acids are bench-stable and readily available chemical feedstocks that function as optimal fundamental synthetic platforms for the construction of C(sp3)–C(sp3) bonds via decarboxylation processes. We present a novel practical protocol decarboxylative alkylation Morita–Baylis–Hillman acetates with various carboxylic photoinduced iron-mediated ligand-to-metal charge transfer (LMCT) process under redox-neutral conditions. This method exhibits remarkable tolerance to wide array acids, including primary, secondary, tertiary obviating requirement preactivated radical precursors. The preliminary mechanistic analyses indicate pathway is involved in this catalytic transformation.

Язык: Английский

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Decatungstate-Catalyzed Hydrosilylation of α-Trifluoromethylalkenes for Construction of α-Trifluoromethyl-β-silanes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 18, 2025

The hydrosilylation of alkenes is a pivotal transformation for the synthesis organosilanes; however, fluorine-containing limited due to facile β-fluoride elimination. Herein, by employing direct hydrogen atom transfer (HAT) catalyst, tetrabutylammonium decatungstate (TBADT), and using disulfide as co-catalyst, we have successfully developed mild photocatalytic α-trifluoromethylalkenes α-trifluoromethyl-β-silanes. Our method features conditions, good regioselectivity, compatibility. elimination was fully inhibited. A radical mechanism proposed based on preliminary results.

Язык: Английский

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Electrochemical Synthesis of gem‐Difluoro‐ and γ‐Fluoro‐Allyl Boronates and Silanes

Chemistry - A European Journal, Год журнала: 2022, Номер 28(66)

Опубликована: Сен. 6, 2022

Abstract The electrochemical synthesis of fluorinated allyl silanes and boronates was disclosed. addition electrogenerated boryl or silyl radicals onto many α‐trifluoromethyl α‐difluoromethylstyrenes in an undivided cell allowed the formation a large panel synthetically useful gem ‐difluoro γ‐fluoroallyl (64 examples, from 31 % to 95 yield). In addition, scale up reactions under continuous flow showcased using reactor with promising volumetric productivity (688 g.L −1 .h 496 ). Moreover, synthetic utility these building blocks highlighted through versatile transformations. Finally, plausible reaction mechanisms were suggested explain products.

Язык: Английский

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Visible-Light-Induced Defluorinative α-C(sp³)–H Alkylation for the Synthesis of gem-Difluoroallylated α-Trifluoromethylamines

Organic Letters, Год журнала: 2023, Номер 25(51), С. 9124 - 9129

Опубликована: Ноя. 17, 2023

Herein, we describe a novel and efficient photoredox catalytic Cα radical addition/defluoroalkylation coupling reaction between α-trifluoromethyl alkenes N-trifluoroethyl hydroxylamine. A series of gem-difluoroallylated α-trifluoromethylamines were synthesized by the addition enabled 1,2-H shift in situ-generated radical. Notably, this protocol is distinguished its mild conditions, easy operation, excellent functional group tolerability.

Язык: Английский

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Copper‐Catalyzed Radical Silylarylation of Activated Alkenes: Preparation of β‐Silyl Amide‐Pharmaceutical Hybrids

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(6), С. 1325 - 1330

Опубликована: Фев. 2, 2024

Abstract Copper‐catalyzed silylarylation of N ‐(arylsulfonyl)acrylamides via a tandem silyl radical addition/1,4‐aryl migration/desulfonylation sequence has been developed. This method employs silanes as the precursor and di‐ tert ‐butyl peroxide (DTBP) initiator. By using this cascade procedure, series β ‐silyl amide‐pharmaceutical hybrids which contain an α ‐all‐carbon quaternary stereocenter were facilely synthesized.

Язык: Английский

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Visible light catalyzed arylsilylation of alkenes to construct silicon-containing 1,1-diaryl moieties

Green Chemistry, Год журнала: 2024, Номер 26(8), С. 4785 - 4791

Опубликована: Янв. 1, 2024

We have developed an efficient photocatalyzed arylsilylation of alkenes, utilizing silylboranes and (hetero)aryl nitriles in the presence base photocatalyst.

Язык: Английский

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