Photoredox radical/polar crossover enables C–H gem-difunctionalization of 1,3-benzodioxoles for the synthesis of monofluorocyclohexenes

Chemical Science, Journal Year: 2023, Volume and Issue: 14(22), P. 6045 - 6051

Published: Jan. 1, 2023

A photocatalytic C-H gem-difunctionalization of 1,3-benzodioxoles with two different alkenes for the synthesis highly functionalized monofluorocyclohexenes is described. Using 4CzIPN as photocatalyst, direct single electron oxidation allows their defluorinative coupling α-trifluoromethyl to produce gem-difluoroalkenes in a redox-neutral radical polar crossover manifold. The bond resultant γ,γ-difluoroallylated was further via addition electron-deficient using more oxidizing iridium photocatalyst. capture situ generated carbanions by an electrophilic gem-difluoromethylene carbon and consecutive β-fluoride elimination afford monofluorocyclohexenes. synergistic combination multiple termination pathways enables rapid incorporation molecular complexity stitching simple readily accessible starting materials together.

Language: Английский

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Advances in photoinduced radical–polar crossover cyclization (RPCC) of bifunctional alkenes

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(3), P. 895 - 915

Published: Dec. 20, 2023

Photoinduced radical–polar crossover cyclization (RPCC) of bifunctional alkenes is high synthetic utility to produce cyclic products with precise alkene design. This review summarizes the recent representative advances in field RPC.

Language: Английский

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Photoinduced radical-polar crossover cyclization reactions

Chem Catalysis, Journal Year: 2024, Volume and Issue: 4(5), P. 100945 - 100945

Published: March 5, 2024

Language: Английский

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Picking Two out of Three: Defluorinative Annulation of Trifluoromethyl Alkenes for the Synthesis of Monofluorinated Carbo‐ and Heterocycles

The Chemical Record, Journal Year: 2024, Volume and Issue: 24(3)

Published: Jan. 22, 2024

Abstract The increasing demand of organofluorine compounds in medicine, agriculture, and materials sciences makes sophisticated methods for their synthesis ever more necessary. Nowadays, not only the C−F bond formation but also selective cleavage readily available poly‐ or perfluorine‐containing have become powerful tools effective compounds. defluorinative cross‐coupling trifluoromethyl alkenes with various nucleophiles radical precursors an S N 2’ manner is a convergent route to access gem ‐difluoroalkenes, which turn react via V‐type reaction. If V reactions occur intramolecularly, dual allows facile assembly monofluorinated cyclic skeletons structural complexity diversity. In this personal account, we summarized advances field on basis coupling cyclization partners, including binucleophiles, alkynes, diradical bearing nucleophilic site. Accordingly, annulation can be achieved by base‐mediated sequential 2′/S reactions, transition metal catalyzed mediated photoredox catalysis, combination photocatalytic context seminal works others field, concise summary contributions authors offered.

Language: Английский

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Photocatalytic Defluorinative Three-Component Reaction of α-Trifluoromethyl Alkenes, Alkenes, and Sodium Sulfinates: Synthesis of Monofluorocyclopentenes

Organic Letters, Journal Year: 2022, Volume and Issue: 24(32), P. 5946 - 5950

Published: Aug. 4, 2022

A photocatalytic three-component reaction of α-trifluoromethyl alkenes, electron-rich and sodium sulfinates for the synthesis gem-difluoroalkenes in a radical/polar crossover manner was developed. Due to strong electron-withdrawing nature sulfonyl group, resultant can be converted into various monofluorocyclopentenes via intramolecular base-mediated SNV reactions one pot.

Language: Английский

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Gem-Difluoroallylation of Aryl Sulfonium Salts

Organic Letters, Journal Year: 2022, Volume and Issue: 24(48), P. 8753 - 8758

Published: Nov. 28, 2022

The unprecedented photochemical late-stage defluorinative gem-difluoroallylation of aryl sulfonium salts, which are formed site-selectively by direct C(sp2)─H functionalization, is herein disclosed. This method distinguished its mild reaction conditions, wide scope, and excellent site-selectivity. As showcase examples, a Flurbiprofen Pyriproxyfen derivatives could be late stage gem-difluoroallylated with high yields. Experimental computational investigations were conducted.

Language: Английский

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A One-Pot Domino Reaction Providing Fluorinated 5,6-Dihydro-1,2-thiazine 1-Oxides from Sulfoximines and 1-Trifluoromethylstyrenes

Organic Letters, Journal Year: 2023, Volume and Issue: 25(9), P. 1569 - 1572

Published: Feb. 28, 2023

N-Trifluoroacetylated (N-TFA) sulfoximines react with 1-trifluoromethylstyrenes in a one-pot domino reaction to give fluorinated 5,6-dihydro-1,2-thiazine 1-oxides good high yields. The process involves three sequential steps that can be characterized as (1) nucleophilic allylic substitution (SN2'), (2) hydrolysis, and (3) intramolecular vinylic (SNV). products further modified by defluorination. molecular structure of the resulting product was confirmed X-ray crystallographic analysis.

Language: Английский

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Synthesis of 2-Fluorobenzofuran by Photocatalytic Defluorinative Coupling and 5-endo-trig Cyclization

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(11), P. 7586 - 7591

Published: May 1, 2023

An alkyl radical-triggered dual C–F bond cleavage of α-CF3-ortho-hydroxystyrenes for the synthesis 2-fluorobenzofurans was developed. The visible-light-induced defluorinative cross-coupling reactions with a variety carboxylic acids produced gem-difluoroalkenes, which underwent SNV-type 5-endo-trig cyclization to give 2-fluorobenzofurans. Mechanistic studies indicated that electron transfer between phenoxyl radicals and carboxylates major pathway generation radicals.

Language: Английский

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Visible-light-mediated C–F bond cleavage for the synthesis of polyfluorinated compounds

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(13), P. 3341 - 3346

Published: Jan. 1, 2023

Herein, we describe a novel and efficient photo-redox catalytic difluorinated ester radical addition/defluoroalkylation coupling reaction between trifluoroacetic acid derivatives α-trifluoromethyl alkenes.

Language: Английский

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Photocatalyzed/Base-Mediated Defluorinative Three-Component Cascade Cyclization: Access to Monofluorocyclohexenes and 6-Fluoro-1,2,3,4-tetrahydropyridines

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 19, 2025

A three-component cascade cyclization of α-CF3 alkenes, electron-rich and dimethyl esters or sulfonamides via a dual C–F bond cleavage process is described. This methodology provides general efficient strategy to access monofluorocyclohexenes 6-fluoro-1,2,3,4-tetrahydropyridines by switching the bifunctional reagents (dimethyl sulfonamides), which are valuable building blocks in synthetic chemistry pharmaceutical industries. The reaction mechanism applications products have been demonstrated.

Language: Английский

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