Picking Two out of Three: Defluorinative Annulation of Trifluoromethyl Alkenes for the Synthesis of Monofluorinated Carbo‐ and Heterocycles

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

---

Radical-mediated [3 + 2 + 1] annulation of α-polyfluoromethyl alkenes with arylisocyanates enabled by C(sp³)–F activation

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(5), P. 1305 - 1313

Published: Jan. 1, 2024

A conceptually novel single electron transfer strategy for C(sp3)–F activation-enabled [3 + 2 1] annulation of α-polyfluoromethyl alkenes is developed.

Language: Английский

---

Modular Synthesis of Monofluorinated 1,2,4-Triazoles/1,3,5-Triazines via Defluorinative Annulations of N-CF₃ Imidoyl Chlorides

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

Published: March 10, 2025

Ring-fluorinated azaheterocycles have wide applications in agrochemicals, pharmaceuticals, and synthesis, which prompt continuous endeavors to expand such heterocyclic families. However, monofluorinated triazaheterocycles hardly been explored. This work reported a novel modular synthesis of 1,2,4-triazoles 1,3,5-triazines, utilizes N-CF3 imidoyl chlorides as unique polyfluoro synthons their defluorinative annulations with hydrazines/imidazines. Further modifications these fluorinated heterocycles highlight the potential method for accessing functional molecules.

Language: Английский

---

Combining Hydrodefluorination and Defluorophosphorylation for Chemo- and Stereoselective Synthesis of gem-Fluorophosphine Alkenes

Organic Letters, Journal Year: 2023, Volume and Issue: 25(34), P. 6368 - 6373

Published: Aug. 18, 2023

A chemo-, regio-, and stereoselective reaction of trifluoromethyl enones, phenylsilane, phosphine oxides through a sequential hydrodefluorination defluorophosphorylation relay is developed for the synthesis distinctive gem-fluorophosphine alkenes. This multicomponent occurred under transition-metal-free conditions with good functional group tolerance. Moreover, preinstalled carbonyl auxiliary important tuning reactivity β-trifluoromethyl thereby enabling controllable selective functionalization two fluorine atoms in trifluoromethylated enones.

Language: Английский

---

Organo-Photoredox Catalyzed gem-Difluoroallylation of Ketone-Derived Dihydroquinazolinones with α-Trifluoromethyl Alkenes via C(sp3)-C Bond and C(sp3)-F Bond Cleavage

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(27), P. 5561 - 5568

Published: Jan. 1, 2024

An organo-photoredox catalyzed defluorinative alkylation of ketone-derived dihydroquinazolinones with α-trifluoromethyl alkenes is described, providing a facile access to diverse set gem -difluoroalkenes.

Language: Английский

---

Visible-light-mediated synthesis of functionalized benzofurans: an update

Chemistry of Heterocyclic Compounds, Journal Year: 2024, Volume and Issue: 60(1-2), P. 1 - 22

Published: Feb. 1, 2024

Language: Английский

---

Transition-Metal-Free Late-Stage Decarboxylative gem-Difluoroallylation of Primary Alkyl Acids

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(20), P. 15234 - 15247

Published: Oct. 8, 2024

A transition-metal-free late-stage decarboxylative gem-difluoroallylation of carboxylic acids with α-trifluoromethyl alkenes has been described by the use organo-photoredox catalysis. Both primary alkyl and heteroaryl were readily incorporated. This approach merits feedstock materials, mild reaction conditions, wide functionality tolerance. The synthetic utility this highlighted functionalization a variety acid-containing natural products drug molecules.

Language: Английский

---

Divergent Synthesis of Benzo[4,5]imidazo[2,1-b][1,3]thiazines and α-Trifluoromethyl-β-arylthio Tertiary Alcohols from 2-Mercaptobenzimidazoles and α-CF₃ Alkenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(44), P. 9610 - 9616

Published: Oct. 25, 2024

An efficient and metal-free approach for the divergent synthesis of 2-fluoro-3-aryl-4H-benzo[4,5]imidazo[2,1-b][1,3]thiazines α-trifluoromethyl-β-arylthio tertiary alcohols from 2-mercaptoimidazoles α-CF3 alkenes has been developed. The chemoselectivity was well controlled by base or light; a series were afforded via base-mediated sequential SN2′- SNV-type reactions. Meanwhile, could be selectively achieved through visible-light-driven electron donor–acceptor (EDA) complex-initiated radical cascade thiolation/hydroxylation in absence base, transition metal, external photocatalyst.

Language: Английский

---

Visible‐light photoredox catalyzed synthesis of tetrahydrobenzofuranone: Oxidative [3 + 2] cycloaddition of dicarbonyl and alkene

Journal of Heterocyclic Chemistry, Journal Year: 2024, Volume and Issue: 61(8), P. 1248 - 1260

Published: May 29, 2024

Abstract Visible‐light‐mediated formation of tetrahydrobenzofuranone by direct oxidative [3 + 2] cycloaddition via coupling between dimedone and chalcone using eosin‐Y as a photoredox catalyst has been reported. The reaction takes place radical pathway evidenced from our experiments literature. developed method involves the utilization visible‐light catalysis for C‐C C‐O bond abstraction methylinic hydrogen β ‐carbon well carbonyl group α‐carbon in one‐pot procedure. present protocol shows significant advantages such application visible light clean source energy, green solvent, mild conditions, cost effectiveness, short time, metal free synthesis, easy operation, high atom economy, broad substrate scope with functional tolerance. Moreover, outstanding yield product obtained up to 82%.

Language: Английский

---

Synthesis of gem-Difluorohomoallyl Amines via a Transition-Metal-Free Defluorinative Alkylation of Benzyl Amines with Trifluoromethyl Alkenes

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(12), P. 8342 - 8356

Published: May 31, 2024

A mild and transition-metal-free defluorinative alkylation of benzyl amines with trifluoromethyl alkenes is reported. The features this protocol are easy-to-obtain starting materials, a wide range substrates, functional group tolerance as well high atom economy, thus offering strategy to access variety

Language: Английский

---