Modular Synthesis of Furans with Four Nonidentical Substituents by Aqueous Defluorinative Reaction of Trifluoromethyl Enones with Two Nucleophiles

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 24, 2024

A three-component reaction of trifluoromethyl enones, phosphine oxides, and alcohols in water solution is developed. This defluorinative occurs through a cascade process involving defluorophosphorylation, defluoroalkyloxylation, defluoroheteroannulation, enabling the modular synthesis furans with four distinct substituents: C2-alkyloxy, C3-trifluoromethyl, C4-phosphoryl, C5-(hetero)aryl groups. Moreover, apart from alcohol substrates, scope nucleophiles could be further extended to phenols, azacycles, or sulfonamide.

Language: Английский

---

Multi-functionalization of β-trifluoromethyl enones enabled 2,3-dihydrofuran synthesis

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(18), P. 5144 - 5150

Published: Jan. 1, 2024

A transition-metal-free multi-functionalization reaction of β-trifluoromethyl enones and azacycles is first developed for the synthesis valuable amino-2,3-dihydrofuran derivatives.

Language: Английский

---

Three-Component Sulfonylation and Heteroannulation Enabled by 3-Fold Defluorofunctionalization of Trifluoromethyl Enones

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 23, 2025

Trifluoromethyl enone emerges as a versatile and multifaceted building block in organic synthesis. A defluorinative heterocyclization reaction of readily available β,β-ditrifluoromethylated enones biocompatible sodium sulfinates has been developed for the modular synthesis densely functionalized furans with regio-defined C2,4-bissulfonyl C3-trifluoromethyl substitutions. This three-component method proceeds through sequential sulfonylation intramolecular O-cyclization, enabling assembly one furan ring, formation C-SO2/C–O bonds, cleavage three C(sp3)-F bonds one-pot manner under transition metal-free conditions. Moreover, obtained product can further react benzyne precursor to generate 1,4-epoxynaphthalene Diels–Alder cycloaddition. The is also distinguished by its broad substrate scope, excellent functional group tolerance, scalability.

Language: Английский

---

Water-Involved 1,3-Aminoxylation of Fluoroalkenes: Chemo-, Regio-, and Stereoselective Synthesis of β-Fluoroacyl Vinylamines

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

Perfluoroalkyl alkenyl iodides (PFAIs) are emerging as highly reactive, storage-stable, and multifunctional fluoroalkyl-bearing reagents, facilitating the manufacture of value-added organofluorides through multi-halo-functionalization. Herein, we developed a water-involved 1,3-aminoxylation PFAIs with sulfonamides for chemo-, regio-, Z-stereoselective synthesis valuable β-fluoroacyl vinylamines. This reaction proceeded via sequential deiodoamination defluoroxylation process under transition-metal-free conditions, featuring broad substrate scope good functional group tolerance. Compared to reported methods, some drawbacks, such multistep manipulation, harsh need expensive catalysts, use toxic/sensitive could be eliminated. Furthermore, synthetic potential this method was demonstrated scale-up synthesis, postfunctionalization complex molecules, ready transformation products.

Language: Английский

---

Metal-Free Catalytic Synthesis of Tetrasubstituted Furans from α-Hydroxy Ketones and Cyano Compounds

Molecules, Journal Year: 2025, Volume and Issue: 30(8), P. 1832 - 1832

Published: April 19, 2025

A novel method for the efficient and straightforward synthesis of tetrasubstituted furans is presented, employing a base-catalyzed reaction α-hydroxy ketones cyano compounds. The proceeds under relatively mild conditions, utilizes readily available starting materials, exhibits good functional group tolerance high yields. Notably, this obviates need expensive metal catalysts introduces crucial groups such as amino moieties. Furthermore, it avoids prerequisite functionalization substrates, thereby enhancing atomic economy.

Language: Английский

---

1,2‐Dichloroethane‐Assisted Defluorinative Ring‐Opening Reaction of DABCO and Polyfluoroalkyl Peroxides: Synthesis of Fluorinated N‐Ethyl Piperazines

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

Published: Nov. 14, 2024

Comprehensive Summary A catalyst‐free and additive‐free ring‐opening reaction of polyfluoroalkyl peroxides, triethylenediamine (DABCO), 1,2‐dichloroethane (DCE) has been developed for the defluorinative synthesis structurally diverse piperazines featuring a fluoroenone framework N ‐chloroethyl‐substituent with high Z ‐stereoselectivity. The success this three‐component is attributed to in situ generation an active 1‐(2‐chloroethyl)‐1,4‐diazabicyclo[2.2.2]octan‐1‐ium (DABCO·DCE) salt, which judiciously acts as formal ‐(2‐chloroethyl)piperazine equivalent coupling less‐studied aliphatic fluorinated substances. Impressively, accomplishes multi‐activation robust C(sp 3 )‐F, )‐Cl, )‐O, )‐N bonds one‐pot process, offering practical platform late‐stage functionalization complex molecules. Furthermore, resulting products can not only serve versatile building blocks heterocycles, but also undergo C—Cl bond displacement transformations ‐, O S ‐nucleophiles.

Language: Английский

---

Heteroarylation of Organophosphonium Salts with Indoles in Water: Synthesis of Symmetrical and Unsymmetrical 3,3'‐Bisindolylmethane Derivatives

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 16, 2024

Abstract A method for the synthesis of symmetrical and unsymmetrical 3,3′‐bis(indolyl)methanes (3,3′‐BIMs) has been developed through direct heteroarylation indolyl‐containing di(hetero)aryl phosphonium salts with indole derivatives in aqueous media. This metal‐free reaction proceeds smoothly under mild conditions, eliminating need hazardous solvents expensive additives/catalysts typically used conventional routes, thereby highlighting synthetic practicality efficiency process. The success this approach is largely attributed to role water as a promoter, facilitating C−P bond functionalization salts. Furthermore, demonstrates broad substrate scope, good functional group tolerance, excellent scalability. Moreover, protocol can also be extended triindolylmethane compound diarylmethylated indole.

Language: Английский

---

Intramolecular/Intermolecular Sequential Cyclization Accompanied by Double C–F Bond Cleavage: Access to Tricyclic Fluorine-Containing Pyrano[3,2-c]chromenes

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(22), P. 16553 - 16563

Published: Oct. 28, 2024

Defluorinative cyclization of CF

Language: Английский

---

Water-enabled α-C(sp³)–H amination via [1,6]-hydride transfer: green access to diazepino[6,5,4-cd]indoles

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Water-enabled α -C(sp 3 )–H amination of 4-dialkylamino-indole-3-carbaldehydes with primary amines was developed for green synthesis diazepino[6,5,4- cd ]indoles via cascade aldimine condensation/[1,6]-hydride transfer/cyclization.

Language: Английский

---