Transition‐Metal‐Mediated Fluoroalkylation of Carbon Electrophiles through Cross‐Electrophile Couplings

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Comprehensive Summary Organofluorine compounds have attracted substantial interest in life and materials sciences due to the unique properties of fluorine atom(s) that often change physicochemical biological organic molecules. Transition‐metal‐mediated cross‐electrophile coupling between carbon electrophiles fluoroalkyl has emerged as a straightforward efficient route for synthesis wide range fluoroalkylated because its synthetic convenience without tedious organometallic reagents. Moreover, alkenes or alkynes‐involved three‐component couplings provide rapid effective access carbonfunctionalized alkanes alkenes. Herein, we comprehensively summarize transition‐metal‐mediated reductive fluoroalkylation diverse through historical perspective, including trifluoromethylation, difluoroalkylation, monofluoroalkylation, so on. Different transition metals (Cu, Ni, etc .) strategies are discussed, which nickel‐catalyzed reactions represent an attractive site‐selectively organofluorine compounds. Key Scientists As early 1965, McLoughlin Thrower finished first stoichiometric copper‐mediated aromatic iodides with iodides. However, excess elevated temperature were used this method. In 1969, Kobayashi Kumadaki reported studies on trifluoromethylation halides trifluoromethyl iodide. After more than four decades, Zhang group developed β ‐fluorinated alkylation (hetero)aryl secondary alkyl bromides 2015, difluoromethylation chlorides chlorodifluoromethane ClCF 2 H 2017. The also enantioselective alkyl‐arylation 3,3,3‐trifluoropropene tertiary 2018, MacMillan novel copper/photoredox dual catalytic system aryl ( S )‐(trifluoromethyl) dimesitylsulfonium triflate presence tris‐(trimethylsilyl) silanol. They nickel/photoredox catalyzed silane. During time, Wang monofluoroalkylation monofluoroalkyl halides. From 2021 2023, same further series trifluoroalkylation aryl, alkenyl, acyl nonfluorinated alkynes could be couplings. Chu fluoroalkyl‐acylation Later, they fluoroalkyl‐arylation unactivated tethering pendant chelating group. 2019, Chaładaj palladium‐catalyzed perfluoroalkyl‐arylation perfluoroalkyl

Language: Английский

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Defluorinative Cyclization of Enamides with Fluoroalkyl Halides Through Two Vicinal C(sp³)─F Bonds Functionalization

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

Published: Dec. 31, 2024

Abstract Introducing distinctive functional groups to expand the structural diversity and improve intrinsic properties of parent molecules has been an essential pursuit in organic chemistry. By using perfluoroalkyl halide (PFAH) as a nontraditional, readily available, ideal 1,2‐difluoroalkenyl coupling partner, defluorinative cyclization reaction enamides for construction fluoroalkenyl oxazoles is first developed. The selective controllable two‐fold cleavage vicinal C(sp 3 )─F bonds PFAH not only enables introduction specific moiety with ease but also results functionalization two 2 )─H without need metal catalyst, photocatalyst, oxidant, or light. method can be applied late‐stage modification complex molecules, synthesis biological‐relevant oxazole analoges, scale‐up synthesis, which all further highlight real‐world utility this protocol. Mechanistic studies reveal that possibly proceeds through radical perfluoroalkylation, consecutive C─F bond heterolytic cleavage, process. In addition, situ formed may serve hydrogen abstractor.

Language: Английский

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The Progress of Reductive Coupling Reaction by Iron Catalysis

The Chemical Record, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 17, 2024

Abstract The transition metal catalyzed coupling reaction has revolutionized the strategies for forging carbon‐carbon bonds. In contrast to traditional cross‐coupling methods using pre‐prepared nucleophilic organometallic reagents, reductive reactions C−C bonds formation provide some advantages. Because both partners are reduced in final products a stoichiometric amount of reductant, this approach not only avoids need use sensitive species, but also provides an orthogonal and complementary access classical reaction. Notably, feature readily available fragments, promote good step economy, exhibit high functional group tolerance unique chemoselectivity, which have propelled their increasingly popular organic synthesis. recent years, due low price, minimal toxicity, environmentally benign character, iron‐catalyzed garnered significant attention from synthetic chemists pharmacologists, especially coupling. This review aims insightful overview advances reactions, illustrate possible mechanisms.

Language: Английский

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Iron-Catalyzed Reductive Cross-Coupling of Heterocyclic Bromides

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7700 - 7709

Published: April 24, 2025

Language: Английский

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Biomimetic C H bond oxidation via non-heme supported iron catalyst

Applied Surface Science, Journal Year: 2024, Volume and Issue: unknown, P. 161616 - 161616

Published: Oct. 1, 2024

Language: Английский

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