Tetrafluoroisopropylation of alkenes and alkynes enabled by photocatalytic consecutive difluoromethylation with CF2HSO2Na

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

Опубликована: Июль 6, 2024

Direct assembly of complex fluorinated motifs from simple fluorine sources is an attractive frontier synthetic chemistry. Reported herein unconventional protocol for achieving tetrafluoroisopropylation by using commercially available CF

Язык: Английский

---

Divergent Generation of the Difluoroalkyl Radical and Difluorocarbene via Selective Cleavage of C–S Bonds of the Sulfox-CF₂SO₂Ph Reagent

Organic Letters, Год журнала: 2024, Номер 26(4), С. 872 - 876

Опубликована: Янв. 18, 2024

A new difluoroalkylation reagent Sulfox-CF2SO2Ph bearing both sulfoximine and sulfone moieties was prepared from commercially available SulfoxFluor PhSO2CF2H. On one hand, the could act as a (phenylsulfonyl)difluoromethyl radical source under photoredox catalysis, in which arylsulfoximidoyl group is selectively removed. other basic conditions, serve difluorocarbene precursor for S- O-difluoromethylations with O-nucleophiles, respectively, phenylsulfonyl removed (followed by α-elimination of group).

Язык: Английский

---

Controllable Double Difluoromethylene Insertions into S−Cu Bonds: (Arylthio)tetrafluoroethylation of Aryl Iodides with TMSCF₂Br

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Фев. 15, 2024

Abstract A new method of constructing “ArSCF 2 CF Cu” from ArSCu and TMSCF Br (TMS=trimethylsilyl) has been developed. The cross‐coupling reactions the obtained with diverse aryl iodides (Ar′I) provide an efficient access to Ar′CF SAr. Mechanistic studies demonstrate that species were generated through controllable double difluoromethylene insertions into ArS−Cu bonds rather than 1,2‐addition tetrafluoroethylene.

Язык: Английский

---

General radical difluoromethylation using difluoroacetic anhydride via photoredox catalysis

Science China Chemistry, Год журнала: 2024, Номер 67(8), С. 2637 - 2646

Опубликована: Июнь 26, 2024

Язык: Английский

---

Advances in the Synthetic Utility of Difluorocarbene Generated from TMSCF₃ (Ruppert‐Prakash Reagent) and Its Derivatives

The Chemical Record, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

Abstract Organofluorine compounds are of pivotal significance particularly, in drug and agrochemical industries different strategies have been designed for their synthesis. The last two decades witnessed the emergence difluorocarbene as an efficient synthetic tool, providing easy access to organofluorine compounds. This review summarises reactions generated from Ruppert‐Prakash reagent (TMSCF 3 ) its derivatives TMSCF 2 Cl Br. Among various fluorination techniques available, chemistry offers a cost effective procedure, opening avenue large number details developments utility derivatives, till date.

Язык: Английский

---

N-Aryl/-Alkenyl difluoroketenimines: transient intermediates for the general synthesis of difluoroalkylated heterocycles

Green Synthesis and Catalysis, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Язык: Английский

---

Direct 1,6-Difluoromethylation of 3-Methyl-4-nitro-5-styryl Isoxazoles by Photoredox-Promoted Radical Addition

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(14), С. 10206 - 10211

Опубликована: Июль 12, 2023

The photoredox-catalyzed 1,6-difluoromethylation of 3-methyl-4-nitro-5-styrylisoxazole with HCF2SO2Na has been developed. Structurally diverse difluoromethylated products were obtained in good yields, and their further transformations also investigated. di-, tri-, monofluoromethylation the substrates compared, yield difluoromethylation was highest. DFT calculations revealed that reaction CF2H radical nucleophilic, transition state activation energy lowest.

Язык: Английский

---

Zinc 1,1,2,2-Tetrafluoroethanesulfinate: A Synthetically Useful Oxidative and Photoredox Source of the 1,1,2,2-Tetrafluoroethyl Radical

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(8), С. 5485 - 5490

Опубликована: Март 30, 2024

1,1,2,2-Tetrafluoroethyl-containing molecules are of potential importance in drug discovery, but the efficient synthesis such compounds is still relatively unexplored due to lack readily available reagents for incorporation HCF2CF2 group. Herein, we introduce a new reagent, zinc 1,1,2,2-tetrafluoroethanesulfinate, which can be useful oxidative tetrafluoroethylation arylboronic acids and heteroarenes as well novel photoredox, three component hydro-tetrafluoroethylation two alkenes complementary reactivity.

Язык: Английский

---

Tetrafluoroethylation of Electron‐Rich Alkenyl Iodides Enabled by in situ Generation of Solvent‐Stabilized “Ligandless” CuCF₂CF₂H

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(12), С. 2684 - 2690

Опубликована: Апрель 23, 2024

Abstract In this study, we have developed a metal‐mediated synthetic method for incorporating the 1,1,2,2‐tetrafluoroethyl (CF 2 CF H) motif into unactivated, electron‐rich alkenyl iodides using cross‐coupling reactions. We discovered that stable Cu(CF H)(PPh Me) 3 complex, while unreactive with these substrates, serves as P‐ligated reservoir formation of solvent‐stabilized “ligandless” and reactive CuCF H species. This transformation occurs upon addition CuBr, which partially scavenges P‐ligand in form CuBr(PPh . The resulting situ generated solvent stabilized system significantly enhances reactivity particularly towards challenging substrates. advancement enables synthesis HCF ‐glycals, well nucleosides/nucleobases arenes.

Язык: Английский

---

Visible‐Light‐Induced Three‐Component Tetrafluoroethyl‐heteroarylation of Alkenes with 1,1,2,2‐Tetrafluoroethanesulfonyl Chloride and Quinoxalin‐2(1H)‐ones

Chemistry - A European Journal, Год журнала: 2023, Номер 29(56)

Опубликована: Июль 19, 2023

1,1,2,2-Tetrafluoroethyl-containing compounds are valuable structures due to their unique physicochemical properties, which have increasing potential application in drug discovery. However, synthetic methods for preparing such rare. Herein, we report the first use of 1,1,2,2-tetrafluoroethanesulfonyl chloride introduce HCF2 CF2 group into organic molecules via a three-component, radical tetrafluoroethyl-heteroarylation alkenes with readily available quinoxalin-2(1H)-ones. This method provides new and facile approach late-stage functionalization biologically active molecules.

Язык: Английский

---