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

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(16), P. 1913 - 1928

Published: April 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.

Language: Английский

---

A review of frustrated Lewis pair enabled monoselective C–F bond activation

Chemical Science, Journal Year: 2024, Volume and Issue: 15(8), P. 2712 - 2724

Published: Jan. 1, 2024

Frustrated Lewis pair (FLP) bond activation chemistry has greatly developed over the last two decades since seminal report of metal-free reversible hydrogen activation. Recently, FLP systems have been utilized to allow monoselective C-F (at equivalent sites) in polyfluoroalkanes. The problem 'over-defluorination' functionalization polyfluoroalkanes (where multiple fluoro-positions are uncontrollably functionalized) a long-standing chemical fluorocarbon for 80 years. mediated is complementary other solutions address and offers several advantages unique opportunities. This perspective highlights some these opportunities places development into context wider effort overcome 'over-defluorination'.

Language: Английский

---

Sulfinate-Promoted Defluorinative Cyclization of Polyfluoroalkyl Tetralones Enabled by Photocatalysis

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

Published: Feb. 3, 2025

A Ru-catalyzed defluorinative cyclization of polyfluoroalkyl tetralones has been developed under visible-light irradiation for the precise assembly γ-pyrones featuring α-perfluoroalkyl and β-fluorine substituents. Selective functionalization five C(sp3)–F bonds at three carbon sites on perfluoroalkyl chain provides a new mode utilizing polyfluorides as versatile synthons to access difficult-to-obtain heterocyclic scaffolds. Moreover, sulfinate salt serves dual roles an oxygen source creating carbonyl group defluorinating promoter.

Language: Английский

---

Defluorinative functionalization approach led by difluoromethyl anion chemistry

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 7, 2025

Language: Английский

---

Chemo-, regio-, and stereoselective tetrafunctionalization of fluoroalkynes enables divergent synthesis of 5-7-membered azacycles

Chemical Science, Journal Year: 2024, Volume and Issue: 15(30), P. 12026 - 12035

Published: Jan. 1, 2024

A 1,2,3,4-tetrafunctionalization of polyfluoroalkynes for the divergent construction 5-7-membered ( E )-1,2-difluorovinyl azacycles is developed.

Language: Английский

---

Applications of Transition Metal-Catalyzed ortho-Fluorine-Directed C–H Functionalization of (Poly)fluoroarenes in Organic Synthesis

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(8), P. 4822 - 4862

Published: April 2, 2024

The synthesis of organic compounds efficiently via fewer steps but in higher yields is desirable as this reduces energy and reagent use, waste production, thus environmental impact well cost. reactivity C–H bonds ortho to fluorine substituents (poly)fluoroarenes with metal centers enhanced relative meta para positions. Thus, direct functionalization without prefunctionalization becoming a significant area research chemistry. Novel selective methodologies functionalize (poly)fluorinated arenes by taking advantage the C–F are continuously being developed. This review summarizes reasons for consequent developments valuable (poly)fluoroarene-containing compounds.

Language: Английский

---

Metallomimetic C–F Activation Catalysis by Simple Phosphines

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 2005 - 2014

Published: Jan. 11, 2024

Delivering metallomimetic reactivity from simple p-block compounds is highly desirable in the search to replace expensive, scarce precious metals by cheap and abundant elements catalysis. This contribution demonstrates that catalysis, involving facile redox cycling between P(III) P(V) oxidation states, possible using only simple, cheap, readily available trialkylphosphines without need enforce unusual geometries at phosphorus or use external oxidizing/reducing agents. Hydrodefluorination aminodefluorination of a range fluoroarenes was realized with good very yields under mild conditions. Experimental computational mechanistic studies show phosphines undergo oxidative addition fluoroaromatic substrate via Meisenheimer-like transition state form fluorophosphorane. undergoes pseudotransmetalation step silane, initial fluoride transfer P Si, give experimentally observed phosphonium ions. Hydride hydridosilicate counterion then leads hydridophosphorane, which reductive elimination product reform phosphine catalyst. behavior analogous many classical transition-metal-catalyzed reactions so rare example both functional mechanistically catalysis main-group element system. Crucially, reagents used are commercially, easy handle, making these realistic prospect wide academic industrial settings.

Language: Английский

---

Photouranium-Catalyzed C–F Activation Hydroxylation via Water Splitting

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: April 9, 2024

The C–F bond is the strongest covalent single (126 kcal/mol) in carbon-centered bonds, which highest electronegativity of fluorine (χ = 4) gives rise to shortest length (1.38 Å) and smallest van der Waals radius (rw 1.47 Å), resulting enormous challenges for activation transformation. Herein, conversion was realized via photouranium-catalyzed hydroxylation unactivated aryl fluorides using water as a hydroxyl source deliver multifunctional phenols under ambient conditions. featured cascade sequences electron transfer (SET)/hydrogen atom (HAT)/oxygen (OAT), highly integrated from excited uranyl cation. *UO22+ prompted splitting mild photoexcitation, caging active oxygen peroxo-bridged manner critical OAT process releasing hydrogen HAT process.

Language: Английский

---

Functional Post-Synthetic Chemistry of Metal–Organic Cages According to Molecular Architecture and Specific Geometry of Origin

Molecules, Journal Year: 2025, Volume and Issue: 30(3), P. 462 - 462

Published: Jan. 21, 2025

Metal–organic cages (MOCs) are discrete supramolecular entities consisting of metal nodes and organic connectors or linkers; MOCs noted for their high porosity processability. Chemically, they can be post-synthetically modified (PSM) new functional groups introduced, presenting attractive qualities, it is expected that properties will differ from those the original compound. This why highly regarded in fields biology chemistry. The present review deals with current PSM strategies used MOCs, including covalent, coordination, noncovalent methods structural benefits. main emphasis this to show what extent under circumstances a MOC designed obtain tailored geometric architecture. Although sometimes unclear when examining systems, particularizing design systematic approaches development characterization families provides insights into structure–function relationships, which guide future developments.

Language: Английский

---

Perfluoroalkyl Editing of Fluoroalkynes: Chemo-, Regio-, and Stereoselective Synthesis of (E)-(2-Amino-fluoroalkenyl)pyrimidines

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

Published: Feb. 26, 2025

A chemo-, regio-, and stereoselective condensation reaction of perfluoroalkyl alkynes (PFAAs), (CH2O)n, (NH4)2CO3 through the cleavage five inert C(sp3)-F bonds at three distinct carbon sites, thereby establishing an unprecedented platform for synthesizing structurally unique (E)-(2-amino-fluoroalkenyl)pyrimidines, is first developed. Remarkably, this features mild conditions, good compatibility with various functional groups, excellent E-stereoselectivity, late-stage modification complex molecules, scalability, versatile synthetic transformations resulting heterocyclic compounds.

Language: Английский

---