Extending the substrate scope of palladium-catalyzed arylfluorination of allylic amine derivatives DOI Creative Commons
Tamás T. Novák,

Thi Cam Tu Nguyen,

Ágnes Gömöry

et al.

Journal of Fluorine Chemistry, Journal Year: 2023, Volume and Issue: 273, P. 110239 - 110239

Published: Dec. 30, 2023

Fluorinated molecules often show superior bioactivity or ADME (absorption, distribution, metabolism, and excretion) properties compared to their non-fluorinated analogues. In fact, 20–30 % of newly approved drugs the majority recently agrochemicals are organofluorine compounds. Unsurprisingly, there is great interest in development new and/or improved processes for fluorine incorporation. Pd-catalyzed arylfluorination alkenes a novel, emerging fluorination method, which simultaneously introduces atom an aryl group into alkene framework. The aim current work was studying, improving, extending literature protocol, originally utilized N-allylated sulfonamide substrates.

Language: Английский

Recent progress in the organoselenium-catalyzed difunctionalization of alkenes DOI
Pei Qu, Gong‐Qing Liu

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Selenium-based catalysts have recently been utilized to facilitate a variety of new organic transformations, owing their intrinsic advantages, including low cost, toxicity, stability in both air and water, strong compatibility with diverse functional groups. The difunctionalization alkenes-the process incorporating two groups onto carbon-carbon double bond-has garnered particular interest within the chemical community its significant applications synthesis. Recently, organoselenium-catalyzed alkenes has emerged as an ideal powerful route obtain high-value vicinal difunctionalized molecules. This review emphasizes recent advancements this rapidly evolving field, focusing on scope, limitations, mechanisms various reactions.

Language: Английский

Citations

1

Thiolative Annulation of N-Benzyl-N-cyanopropiolamides Leading to Divergent Synthesis of Pyrroloquinazolin-1-ones and Maleimides DOI
Chada Raji Reddy,

Anootha Neeliveettil,

Uprety Ajaykumar

et al.

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

Published: May 8, 2025

An unprecedented successive radical-promoted thiolative annulation/Pd-catalyzed C-H amination of N-benzyl-N-cyanopropiolamides to access pyrrolo[2,1-b]quinazolin-1(9H)-ones in a one-pot manner is described. Moreover, altering the step with oxidation (reagent switch) offered maleimides from same set readily accessible precursors. Both transformations display versatility across wide range substrates, enabling efficient various functionalized quinazolin-1-ones and good yields.

Language: Английский

Citations

0

Multi-substituted trifluoromethyl alkene construction via gold-catalyzed fluoroarylation of gem-difluoroallenes DOI Creative Commons
Zhiqiang Li,

Haijun Tang,

Zaixin Wang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(10), P. 3524 - 3529

Published: Jan. 1, 2024

A visible-light-promoted gold-catalyzed fluoroarylation of gem -difluoroallenes is developed. This reaction proceeds in a highly stereo- and regioselective manner enables facile construction tri- tetra-substituted trifluoromethyl alkenes.

Language: Английский

Citations

2

C–F bond functionalizations via fluorinated carbenes DOI

Yingmei Li,

Jiangbin Luo, Yaojia Jiang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(22), P. 5782 - 5804

Published: Jan. 1, 2023

This feature article summarizes the developments in fluorinated carbene transformations, and their consequent C–F functionalization a cascade platform.

Language: Английский

Citations

5

Fluoroarylation ofgem-difluorostyrenes through a Pd-catalysed aryl C–H bond activation cascade DOI
Lei Chen, Jun Pu, Peng Ye

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(18), P. 4637 - 4642

Published: Jan. 1, 2023

A novel fluoroarylation of gem -difluorostyrenes with AgF and (hetero)arenes through a Pd( ii )-catalysed C(aryl)–H activation cascade was developed, constituting an efficient method to access CF 3 -substituted fluorenes 1,1-diarylmethanes.

Language: Английский

Citations

3

Fluorinated Vinyl Sulfonium Salts and Their Synthetic Utilization DOI
Takeshi Hanamoto

The Chemical Record, Journal Year: 2023, Volume and Issue: 23(9)

Published: Feb. 6, 2023

The fluorinated building block strategy and the direct fluorination are of great importance for synthesis new molecules. These strategies complement each other can be combined to develop a methodology construction wide variety fascinating organofluorine compounds. In our opinion, versatile blocks used in this method should satisfy following conditions: 1) readily prepared from commercially available reagents; 2) easy handle; 3) storage under ordinary conditions without noticeable decomposition; 4) applicability. Based on aforementioned requirements, we focused use vinyl sulfonium salts. This brief review describes five types salts their reactions. Especially, featured typical groups containing trifluoromethyl (CF3 ), difluoromethyl (CF2 H), monofluoromethyl (CFH2 monofluoro (F) or β-bromotetrafluoroethyl (BrCF2 CF2 ) moieties combination with

Language: Английский

Citations

2

Z-Selective access to α-trifluoromethyl arylenes through Pd-catalysed fluoroarylation of 1,1-difluoroallenes DOI
Lei Chen,

Ze-Feng Luo,

Peng Ye

et al.

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(45), P. 8979 - 8983

Published: Jan. 1, 2023

The synthesis of stereo-defined α-trifluoromethyl arylenes is great importance in medical chemistry, organic and materials science. However, despite the recent advances, Z-selective formation has remained underdeveloped. Here, we describe a facile approach towards Z-α-trifluoromethyl through Pd-catalysed stereoselective fluoroarylation 1,1-difluoroallenes presence bulky monophosphine ligand.

Language: Английский

Citations

2

A Convenient Synthesis of Some Phenyl‐Substituted Aliyclic β‐Amino Esters and β‐Lactams DOI Creative Commons

Melinda Nonn,

László Drahos, Lóránd Kiss

et al.

ChemistrySelect, Journal Year: 2023, Volume and Issue: 8(47)

Published: Dec. 15, 2023

Abstract A convenient synthetic procedure has been developed for the access of phenyl‐substituted alicyclic β‐amino acid derivatives. The substrate‐directed palladium‐catalyzed cross‐coupling phenylboronic with five‐ or six‐membered cycloalkene esters and bicyclic β‐lactams in presence Selectfluor as oxidant provided azetidin‐2‐ones. Phenylations were investigated under various experimental conditions different ligands solvent systems. structural architecture starting compounds position their ring olefin bond influenced predetermined structure products.

Language: Английский

Citations

2

DFT Studies on the Mechanisms of Carboamination/Diamination of Unactivated Alkenes Mediated by Pd(IV) Intermediates DOI
Si‐Cong Liu, De‐Cai Fang

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(20), P. 14540 - 14549

Published: Sept. 29, 2023

Density functional theory (DFT) calculations have been employed to investigate the mechanism of carboamination and diamination unactivated alkenes mediated by Pd(IV) intermediates. Both reactions share a common intermediate, serving as starting point for either or pathway. The formation this intermediate encompasses transition state that substantially impacts turnover frequency (TOF) catalytic cycles, with an apparent activation free-energy barrier 26.1 kcal mol-1. Carboamination proceeds through coordination toluene molecule, C-H activation, inner reductive elimination, separation product from while involves ion nucleophile, SN2 attack, product. A comparison profiles can elucidate origin chemoselectivity, Bader's atoms in molecules (AIM) wave function analyses performed analyze contributions outer C-N bonding process.

Language: Английский

Citations

1

Computational and Mechanistic Studies of Pd-Catalyzed Alkene Carboacylation via Ester C–O Bond Activation DOI
Melisa Alkan,

Haley K. Banovetz,

Mark S. Gordon

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9766 - 9776

Published: July 11, 2023

Computational and mechanistic studies of Pd-catalyzed alkene carboacylation via ester bond activation are investigated through a combination density functional theory (DFT) second order perturbation (MP2) calculations experimental methods. The key elementary steps the catalytic cycle, oxidative addition, migratory insertion, transmetalation, reductive elimination, examined. In this paper, we propose novel mechanism for title reaction; indicate that Pd(II) intermediate preceding insertion is cationic as opposed to neutral metal species previously proposed in these types reactions. new organoboron has been identified competent nucleophile transition metal-catalyzed reaction. Analysis competing Suzuki coupling pathways reveals pathway be more energetically favorable with appropriate selection arylboron reagent. Experimental control consistent computational findings.

Language: Английский

Citations

0