Photocatalytic Generation of β-Fluoroalkylated α-Carbonyl Carbocations DOI

Chong‐Jin Zhang,

Zhenzhen Liu,

Yan‐Biao Kang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

Nucleophilic addition to α,β-unsaturated carbonyl compounds normally occurs at the carbon or β-carbon. The direct α-nucleophilic α-carbon can hardly be achieved due electronic mismatch. In this work, we report nucleophilic of β-fluoroalkyl α-carbonyl carbocations that are prepared via CBZ6-induced redox-neutral photocatalysis. process, photocatalytic oxidation radical corresponding carbocation is key step. generated in situ by a polyfluoroalkyl radical, which fragmentation sulfonyl chloride, carbonyls. high E00 value CBZ6 (3.19 V vs saturated calomel electrode), corresponds with absorbed photoenergy, contributes catalytic reactivity.

Language: Английский

Photoredox radical/polar crossover enables C–H gem-difunctionalization of 1,3-benzodioxoles for the synthesis of monofluorocyclohexenes DOI Creative Commons
Jiabao Tian, Lei Zhou

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

Citations

33
Picking Two out of Three: Defluorinative Annulation of Trifluoromethyl Alkenes for the Synthesis of Monofluorinated Carbo‐ and Heterocycles DOI
Jiahao Ling, Lei Zhou

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

Citations

10
Radical Brook rearrangement: past, present, and future DOI
Yunxiao Zhang, Gang Zhou, Shanshan Liu

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review aims to provide an overview of radical Brook rearrangement, which is organized by grouping three type reactive species generated via the unique rearrangement process.

Language: Английский

Citations

1
Copper-Catalyzed 1,4-Trifluoromethylthio-Arylsulfonylation of 1,3-Enynes via the Insertion of Sulfur Dioxide DOI

Hongzhuo Song,

Xuemei Zhang, Gang Chen

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(31), P. 5916 - 5921

Published: July 27, 2023

A copper-catalyzed trifluoromethylthio-arylsulfonylation between 1,3-enynes, AgSCF3, aryldiazonium tetrafluoroborates, and SO2 (from SOgen) is presented, which could introduce sulfone, SCF3, allene moieties into one molecule simultaneously. This strategy features mild reaction conditions, good substrate compatibility, excellent regioselectivity. The products obtained have the potential for further conversion other valuable compounds. Initial investigations mechanism suggest that it may proceed via a radical pathway. Notably, SOgen was proven as uniquely effective surrogate in this transformation.

Language: Английский

Citations

17
Selective and Controllable Defluorophosphination and Defluorophosphorylation of Trifluoromethylated Enones: An Auxiliary Function of the Carbonyl Group DOI

Li-Wen Sun,

Ya‐Fei Hu,

Wen-Jun Ji

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(20), P. 3745 - 3749

Published: May 11, 2023

The auxiliary function of a carbonyl group in the tunable defluorophosphination and defluorophosphorylation trifluoromethylated enones with P(O)-containing compounds was demonstrated. Controlled replacement one or two fluorine atoms while maintaining high chemo- stereoselectivity achieved under mild conditions, thus enabling diversity-oriented synthesis skeletally diverse organophosphorus libraries─(Z)-difluoro-1,3-dien-1-yl phosphinates, (1Z,3E)-4-phosphoryl-4-fluoro-buta-1,3-dien-1-yl (E)-4-phosphoryl-4-fluoro-1,3-but-3-en-1-ones─in good yields excellent functional tolerance.

Language: Английский

Citations

14
Transition‐Metal‐Free Allylic Defluorination Cross‐Electrophile Coupling Employing Rongalite DOI
Xiang‐Long Chen, Chun‐Yan Wu, Dong‐Sheng Yang

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(12), P. 1360 - 1366

Published: Feb. 23, 2024

Comprehensive Summary The conversion of CF 3 ‐alkenes to gem ‐difluoroalkenes using reductive cross‐coupling strategy has received much attention in recent years, however, the use green and readily available reducing salt mediate these reactions remains be explored. In this work, a concise construction gem‐ difluoroalkenes, which requires neither catalyst nor metal agent, was established. Rongalite, safe inexpensive industrial product, employed as both radical initiator reductant. This procedure compatible with linear cyclic diaryliodonium salts, enabling wide variety substrates (>70 examples). utility approach demonstrated through gram‐scale synthesis efficient late‐stage functionalizations anti‐inflammatory drugs.

Language: Английский

Citations

4
Design and Preparation of Heterostructured Cu2O/TiO2 Materials for Photocatalytic Applications DOI Creative Commons

Yating Tai,

Boxuan Yang, Jing Li

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(21), P. 5028 - 5028

Published: Oct. 24, 2024

The extensive use of fossil fuels has sped up the global development world economy and is accompanied by significant problems, such as energy shortages environmental pollution. Solar energy, an inexhaustible clean resource, emerged a promising sustainable alternative. Light irradiation can be transformed into electrical/chemical which used to remove pollutants or transform contaminants high-value-added chemicals through photocatalytic reactions. Therefore, photocatalysis strategy overcome increasing problems. As well-known, photocatalysts are key components systems. Among widely investigated photocatalysts, titanium dioxide (TiO

Language: Английский

Citations

4
Synthesis of fluorine-containing bicyclo[4.1.1]octenes via photocatalyzed defluorinative (4+3) annulation of bicyclo[1.1.0]butanes with gem-difluoroalkenes DOI Creative Commons
Kuan Zhang,

Zhengyang Gao,

Yan Xia

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

This manuscript presents a photoredox-catalyzed defluorinative (4 + 3) annulation of bicyclo[1.1.0]butanes with gem -difluoroalkenes, providing practical and straightforward access to the fluorine-containing bicyclo[4.1.1]octenes.

Language: Английский

Citations

4
Synthesis of α-SF5 Ketones by Oxypentafluorosulfanylation of Alkynes with SF5Cl and Oxygen DOI
Xinqiang Tan,

Yuezhen Li,

Ziyou Hao

et al.

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

Published: March 18, 2025

Herein for the first time, we disclose a practical and straightforward approach to access α-SF5 ketones via direct oxypentafluorosulfanylation of alkynes with SF5Cl oxygen under acidic conditions by one step. The protocol features mild reaction conditions, broad substrate scope, good functional group compatibility can be applied late-state functionalization complex natural products pharmaceuticals. A radical mechanism involving SF5 addition triple bonds followed O2 capture is proposed.

Language: Английский

Citations

0
Light‐Induced Domino and Multicomponent Reactions: How to Reach Molecular Complexity without a Catalyst DOI Creative Commons
Polyssena Renzi, Jacopo Scarfiello, Alberto Lanfranco

et al.

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: unknown

Published: Aug. 31, 2023

Abstract Achieving high molecular complexity can be not trivial, but the exploitation of domino reactions provides an atom‐ and step‐economical method to reach this target. Over past decades, a lot efforts have been put on development photocatalytic cascades employing both metal‐based purely organic catalysts. Despite effectiveness these protocols, catalyst‐ additive‐free light‐induced are gaining momentum thank their efficiency, operational simplicity sustainability. The increasing number papers published field in last years is proof appeal transformations. In Review, we discuss multicomponent mediated by light with focus photocatalyst‐ processes. most recent advances synthesis complex nitrogen‐, oxygen‐, sulphur‐ selenium‐heterocycles together analysed emphasis experimental mechanistic studies.

Language: Английский

Citations

10