Synthesis of <i>gem</i>-difluoroalkenes <i>via</i> nickel-catalyzed allylic defluorinative reductive cross-coupling of trifluoromethyl alkenes with epoxides

Lu, Xia; Jiang, Run-Chuang; Li, Jiamei; Liu, Chuang-Chuang; Wang, Qingqing; Zhou, Hongyou

doi:10.1039/d0ob00535e

Cited by 28 publications

(5 citation statements)

References 51 publications

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“…In 2020, Lu (Scheme 28) [45] and Wang (Scheme 29) [46] separately described a reductive defluorinative coupling reaction with trifluoromethyl alkenes employing epoxides as the electrophilic coupling partner. With the aid of Zn as the reductant, a broad array of functionalized gem ‐difluoroalkene‐containing alcohol compounds were synthesized via sequential ring‐opening radical addition and β ‐F elimination.…”

Section: Defluorinative Functionalization Of Trifluoromethylalkenesmentioning

confidence: 99%

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

2021

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Fluorine-containing moieties are widely used in the pharmaceutical, agrochemical, and material fields. Thus, these structures are of immense interest in the fields of organic synthesis and medicinal chemistry. Among various fluorinated groups, the difluoromethyl unit has drawn increasing attention due to its unique pharmaceutical properties. In recent years, several methods for the synthesis of difluoromethylated compounds have been rapidly developed. However, most of these methods treat aromatic compounds with excess difluoromethylating reagents, which often contain organometallic compounds, so these transformations are generally less environmentally friendly and atom-economical. In this review, we summarize the recent development of new methods for the synthesis of difluoromethyl motifs or difluoroalkenes from trifluoromethylated aromatic compounds or trifluoromethyl alkenes via single C(sp 3 )À F bond cleavage.1.

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Section: Defluorinative Functionalization Of Trifluoromethylalkenesmentioning

confidence: 99%

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

2021

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“…and catalysts (e.g., Ni, Ti, Cr, Fe, Co, etc.). [8] Afterward, new methods under photoredox-catalyzed conditions along with organic reducing agent (e.g., silanol, amine, Hantzsch ester, etc.) have been developed, and a series of gem-difluoroalkenes can be synthesized.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Transition‐Metal‐Free Allylic Defluorination Cross‐Electrophile Coupling Employing Rongalite

Chen,

Wu,

Yang

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryThe conversion of CF3‐alkenes to gem‐difluoroalkenes using reductive cross‐coupling strategy has received much attention in recent years, however, the use of green and readily available reducing salt to mediate these reactions remains to be explored. In this work, a concise construction of gem‐difluoroalkenes, which requires neither a catalyst nor a metal reducing agent, was established. Rongalite, a safe and inexpensive industrial product, was employed as both a radical initiator and reductant. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates (>70 examples). The utility of this approach was demonstrated through gram‐scale synthesis and efficient late‐stage functionalizations of anti‐inflammatory drugs.

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“…The authors have cited additional references within the Supporting Information. [18][19][20][21][22][23][24][25][26]…”

Section: Supporting Informationmentioning

confidence: 99%

N‐Directed defluorinative γ‐C(sp³)−H allylation of sulfamate esters for synthesis of gem‐difluoroalkenes via photoredox catalysis

Yang,

Li,

Tan

et al. 2024

Eur J Org Chem

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gem‐Difluoroalkenes are unique structural motifs with important applications ranging from drugs to materials. Herein, we report a novel radical‐mediated defluorinative allylation of sulfamate esters with α‐trifluoromethyl alkenes through distal C(sp3)−H functionalization under photoredox conditions. The reaction could readily incorporate various gem‐difluoroalkene motifs into previously unfunctionalized sp3 carbon centers. The transformation allows directly dual activation of N−H and C(sp3)−H bonds via a photocatalytic and redox‐neutral process, as well as using water as environmentally friendly co‐solvent. The reaction could provide a general and operationally simple method to access gem‐difluoroalkene compounds with high diversity.

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Synthesis of gem-difluoroalkenes via nickel-catalyzed allylic defluorinative reductive cross-coupling of trifluoromethyl alkenes with epoxides

Abstract: A nickel-catalyzed defluorinative reductive cross-coupling of trifluoromethyl alkenes with epoxides has been developed.

Cited by 28 publications

References 51 publications

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

Transition‐Metal‐Free Allylic Defluorination Cross‐Electrophile Coupling Employing Rongalite

N‐Directed defluorinative γ‐C(sp³)−H allylation of sulfamate esters for synthesis of gem‐difluoroalkenes via photoredox catalysis

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Synthesis of gem-difluoroalkenes via nickel-catalyzed allylic defluorinative reductive cross-coupling of trifluoromethyl alkenes with epoxides

Abstract: A nickel-catalyzed defluorinative reductive cross-coupling of trifluoromethyl alkenes with epoxides has been developed.

Cited by 28 publications

References 51 publications

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

Transition‐Metal‐Free Allylic Defluorination Cross‐Electrophile Coupling Employing Rongalite

N‐Directed defluorinative γ‐C(sp3)−H allylation of sulfamate esters for synthesis of gem‐difluoroalkenes via photoredox catalysis

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N‐Directed defluorinative γ‐C(sp³)−H allylation of sulfamate esters for synthesis of gem‐difluoroalkenes via photoredox catalysis