Recent Advances in the Electrochemical Defluorinative Transformations of C—F Bonds

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(16), С. 1913 - 1928

Опубликована: Апрель 24, 2024

Comprehensive Summary Organic fluorine compounds are ubiquitous and pivotally important organic molecules, yet their activation transformation have long been a formidable challenge due to the high energy low reactivity of C—F bonds. electrosynthesis, an environmentally benign synthetic method in chemistry, enables myriad chemical transformations without need for external redox reagents. In recent years, electrochemistry has emerged as powerful tool achieving bonds fluorine‐containing compounds. This review aims succinctly recapitulate latest advancements electrochemical defluorinative delve into reaction design, mechanistic insights, developmental prospects these methods. Key Scientists 1959, Lund was first pioneer electroreduction CF 3 CH group. Electrochemistry lately provided new opportunities efficient conversion fluorides. 2020, Zhou coworkers discovered carboxylation α‐CF alkenes. Lambert colleagues reported electrophotocatalytic amination aryl Electrochemical hydrodefluorination trifluoromethylketones developed by Lennox 2021. same year, Wang Guo disclosed radical alkylation alkenes with Katritzky salts alkyl precursors. Subsequently, Wu Liao described transition‐metal‐free, site‐selective arylation polyfluoroarenes (het)arenes using paired electrophotocatalysis. 2023, numerous efforts were made achieve bond activation. Xia organoboron‐controlled chemoselective sequential (deutero)hydrodefluorination trifluoroacetamides.

Язык: Английский

---

Recent advances in N-heterocyclic carbene (NHC)-catalyzed fluorination and fluoroalkylation

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(7), С. 2112 - 2133

Опубликована: Янв. 1, 2024

Organofluorine compounds are of high value. NHC-catalyzed fluorination and fluoroalkylation have served as powerful versatile vehicles for accessing the related organofluorines. This review focuses on recent developments in this area.

Язык: Английский

---

“On-water” defluorinative cyclization of trifluoromethyl enones with phosphine oxides: synthesis of polysubstituted furans

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 3974 - 3981

Опубликована: Янв. 1, 2024

A defluorinative cyclization of readily available trifluoromethyl enones with phosphine oxides for the synthesis polysubstituted furans is developed in a pure water solution.

Язык: Английский

---

Stereoselective hydrodefluorination of CF₃-substituted alkenes and gem-difluoroalkenes by H⁻

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(5), С. 1388 - 1394

Опубликована: Янв. 1, 2024

Zn-catalyzed stereoselective hydrodefluorination of CF 3 -substituted alkenes, gem -difluoroalkenes and polyfluoroarenes by hydride ion addition has been realized through controlled C(sp )–F and/or 2 bonds cleavage.

Язык: Английский

---

Water-promoted defluorinative synthesis of fluoroalkylated 1,5-diazapentadienes by using (NH₄)₂CO₃ as an NH₂ and NH source

Green Chemistry, Год журнала: 2023, Номер 25(23), С. 9672 - 9679

Опубликована: Янв. 1, 2023

A H 2 O-promoted and (NH 4 ) CO 3 -enabled defluoroiminization reaction of fluoroalkyl alkenes for the synthesis fluoroalkylated 1,5-diazapentadienes has been developed.

Язык: Английский

---

Diastereo- and Enantioselective Dearomative Reductive Aryl-Fluoroalkenylation of Indoles by Nickel Catalysis

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 6432 - 6439

Опубликована: Апрель 11, 2024

Herein, we disclose a nickel-catalyzed dearomative reductive aryl-fluoroalkenylation of indoles by defluorinative coupling with gem-difluoroalkenes. The catalytic protocol affords facile assembly various monofluoroalkene-containing polycyclic fused indolines bearing two contiguous carbon stereocenters in high diastereo- and enantioselectivities tolerance diverse functional groups.

Язык: Английский

---

α,α-Difluorinated Allylsulfones: gem-Difluoroethylenyl Reagents for Synthesis of Fluorinated Chiral α-Quaternary Amino Acids

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 25, 2025

Among numerous fluorine-containing molecules, chiral gem-difluoroethylenes (C═CF2) exhibited unique properties in agrochemicals, pharmaceuticals, and materials science. However, the general synthetic methods were limited to functionalization/defluorination of trifluoromethylalkenes. Here, we disclose a new type difluoroethylenyl reagent, α,α-difluoro allylsulfones, which allows highly enantioselective Cu-catalyzed desulfonylative SN2′ substitution with benzylideneamino esters. This protocol presents novel strategy for construction diversified α-quaternary amino acid derivatives containing gem-difluoroethylene moiety excellent results (up 86% yield, generally 90–98% ee). The ease synthesis applications this protocol, transformations products revealed potential utility chemistry.

Язык: Английский

---

Precision Propargylic Substitution Reaction: Pd-Catalyzed Suzuki–Miyaura Coupling of Nonactivated Propargylamines with Boronic Acids

The Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Авг. 31, 2024

Palladium-catalyzed Suzuki–Miyaura cross-coupling is an efficient approach for C–C bond construction. Here we report a deaminative reaction to achieve chemo- and regioselectivity in the of nonactivated propargylamines with boronic acids, which methyl propiolate introduced promote cleavage C–N form bond. This method features wide range substrates, good functional group tolerance, ease operation, providing alternative accessing valuable propargylated aromatic compounds.

Язык: Английский

---

Regio-, stereo-, and enantioselective ipso- and migratory defluorinative olefin cross-coupling to access highly functionalized monofluoroalkenes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Сен. 2, 2024

Monofluoroalkenes serve as nonhydrolyzable mimetics of amides and are frequently encountered in drug candidates. Herein we report a regio-, enantio-, stereoselective NiH-catalyzed ipso- migratory defluorinative olefin cross-coupling employing readily available olefins gem-difluoroalkenes under mild conditions. This approach enables the efficient synthesis broad array structurally diverse monofluoroalkenes bearing tertiary allylic stereogenic center. Mechanistically, challenging process is successfully realized through ligand relay catalytic strategy, enabling formal C(sp3)–H/C(sp2)–F activation with high levels stereo-, enantiocontrol. Herein, authors

Язык: Английский

---

Catalytic C(sp2)–C(sp3) Cross-Electrophile Coupling in the PtII–NaI–С2Н3I–СН3I–Acetone System

Kinetics and Catalysis, Год журнала: 2024, Номер 65(1), С. 30 - 39

Опубликована: Фев. 1, 2024

Язык: Английский

---