Switchable Nucleophilic Site Enables Expedient Synthesis of CF3-Containing Thiazoles and Allenes from 1,3-Enynes DOI
Xiangyu Li, Na Li, Lan Yang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(19), P. 12755 - 12765

Published: Sept. 15, 2023

Typically, trimethylsilyl isothiocyanate (TMSNCS) is used as a nucleophilic thiocyanate building block (−S–C≡N) that reacts with various electrophiles. However, it has been less explored source of isothiocyanates (−N═C═S), which can usually be converted by thermal isomerization allyl or propargyl thiocyanates. Achieving method precise site control even more challenging. Here, we demonstrate an approach uses metal catalysts to switchable sites and provide strategy construct CF3-containing thiazoles allenes via the multicomponent reaction 1,3-enynes, TMSNCS, electrophilic trifluoromethyl reagent. In presence inexpensive Fe(III) Cu(II) catalysts, current practical convenient, compatible substrates bearing sensitive functional groups readily transferred complex scaffolds. The biological evaluation showed two developed exhibited dramatic inhibitory activities for three human cancer cell lines beyond those 5-fluorouracil. Both compounds increased level reactive oxygen species in MCF-7 cells, believed early step tumor apoptosis.

Language: Английский

Photoinitiated anti‐Hydropentafluorosulfanylation of Terminal Alkynes DOI
Mélodie Birepinte, Pier Alexandre Champagne, Jean‐François Paquin

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(1)

Published: Oct. 30, 2021

A photoinitiated anti-hydropentafluorosulfanylation of terminal alkynes using SF5 Cl and (TMS)3 SiH as the hydrogen atom donor is reported. This transformation generates selectively (Z)-(1-alken-1-yl)pentafluoro-λ6 -sulfanes (Z:E : >85:15), thus allowing preparation this previously unknown geometrical isomer. DFT calculations highlight that selectivity due to intrinsic preference -substituted vinylic radicals adopt a cis geometry, increased steric contacts during transition structures leading minor (E)-products.

Language: Английский

Citations

46
Electrosynthesis of CF3‐Substituted Polycyclic Quinazolinones via Cascade Trifluoromethylation/Cyclization of Unactivated Alkene DOI
Lei Liu,

Wangqin Zhang,

Chao Xu

et al.

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(7), P. 1319 - 1325

Published: Feb. 23, 2022

Abstract An atom and step economy cascade trifluoromethylation/cyclization of unactivated alkene with Langlois reagent as a CF 3 source is described. A variety polycyclic quinazolinones were successfully synthesized in 52–81% yields under transition metal‐ oxidant‐free conditions. The used this strategy possesses the advantages bench‐stablity, cost‐effectivity high‐efficiency. Additionally, gram‐scale reaction, broad substrate scope good functional group tolerance demonstrated synthetic usefulness protocol. magnified image

Language: Английский

Citations

36
Progress in the Electrochemical Reactions of Sulfonyl Compounds DOI
Wangsheng Liu, Hao Lin, Junmin Zhang

et al.

ChemSusChem, Journal Year: 2022, Volume and Issue: 15(7)

Published: Feb. 17, 2022

Abstract Electrosynthesis has recently attracted more and attention due to its great potential replace chemical oxidants or reductants in molecule‐electrode electron transfer. Sulfonyl compounds such as sulfonyl hydrazides, sulfinic acids (and their salts), halides have been discovered practical precursors of several radicals. As electrochemical redox reactions can provide green efficient pathways for the activation compounds, studies electrosynthesis rapidly increased. Several types radicals be generated from anodic oxidation cathodic reduction initiate fluoroalkylation, benzenesulfonylation, cyclization rearrangement. In this Review, we summarize developments involving mainly last decade.

Language: Английский

Citations

33
Synthesis of Secondary Trifluoromethylated Alkyl Bromides Using 2-Bromo-3,3,3-trifluoropropene as a Radical Acceptor DOI
Peng Guo,

Maoling Tao,

Wenwen Xu

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(11), P. 2143 - 2148

Published: March 11, 2022

Herein, the first example using commercially available 2-bromo-3,3,3-trifluoropropene (BTP) as a radical acceptor has been reported. Taking advantage of this strategy, wide range secondary trifluoromethylated alkyl bromides were synthesized in good to excellent yields with broad functional group tolerance by redox-active esters precursor. The practicality protocol was further demonstrated diverse derivations and direct modification biologically active molecules.

Language: Английский

Citations

30
Electrochemical Dearomatization of Indoles: Access to Diversified Fluorine-Containing Spirocyclic Indolines DOI

Kangdong Mo,

Xiaocong Zhou,

Ju Wu

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(15), P. 2788 - 2792

Published: April 11, 2022

A robust and green electrochemical dearomatization of indoles was developed by merging a fluorine-containing group to an indole nucleus under oxidant-free conditions, delivering diverse array tri- difluoromethylated 3,3-spiroindolines with good functional tolerance.

Language: Английский

Citations

29
Direct Perfluoroalkylation of C−H Bonds in (Hetero)arenes DOI

Hajar Baguia,

Gwilherm Evano

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(41)

Published: May 11, 2022

Abstract Perfluoroalkylated (hetero)arenes represent an extremely important family of molecules commonly utilized in many areas such as medicinal chemistry, agrochemistry and material sciences. Due to their unique properties, they have attracted significant interest from synthetic chemists various methods been developed for synthesis. Among them, the direct perfluoroalkylation C(sp 2 )−H bonds is one most attractive straightforward ones, provided that it proceeds with high levels regioselectivity. In this review article, a comprehensive overview advances field presented, special focus on reaction mechanisms involved these transformations All available classified according nature perfluoroalkyl chain introduced, trifluoromethylation reactions being overviewed separate section, reagents/catalysts required.

Language: Английский

Citations

29
Recent Advances in Electrochemical Cascade Cyclization Reactions DOI
Cai Zhang, Yunyun Liu,

Demao Chen

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 55(18), P. 2911 - 2925

Published: Feb. 20, 2023

Abstract This review highlights recent progress in electrochemical cascade cyclization reactions for the synthesis of carbon rings and heterocycles, such as pyridines, quinolines, phenanthridines, cinnolines, 1,4-dihydroquinolines, oxindoles, imidazo[1,5-α]pyridines, imidazoles, etc. The works included herein are introduced two major sections heterocycle construction carbocycle reactions, covering reported from 2012 to 2022. 1 Introduction 2 Electrochemical Cascade Cyclization Synthesis Heterocycles 2.1 Pyridines, Quinolines, Phenanthridines, Cinnolines 2.2 1,4-Dihydroquinolines, Hexacyclic Sulfonamides, Thiazines 2.3 Hydroisoquinolinones Hydroquinolinones 2.4 Quinazolin-4(3H)-ones 2.5 4H-3,1-Benzoxazines 2.6 Oxindoles 2.7 Indolines Indoles 2.8 Imidazo[1,5-α]pyridines Imidazoles 2.9 Imidazolones, Imidazolidinones, Oxazolones, Oxazolidinones 2.10 Benzoxazoles, Oxazolines, Isoxazolines 2.11 Furans Dihydrofurans 2.12 Indolizines, Pyrazoles, Triazolium Inner Salts 2.13 Sulfonated Benzothiophenes, Thiazoles, Dihydrothiazoles, 1,3,4-Thiadiazoles 2.14 Lactones 3 Construction Carbocycles 3.1 Carbon Polycycles Spiroindenes 3.2 Difluoroacyl (Hetero)arenes Indenones 4 Conclusion

Language: Английский

Citations

22
Mediator-free electrochemical trifluoromethylation: a cascade approach for the synthesis of trifluoromethylated isoxazolines DOI
Kingshuk Mahanty, Suman Kumar Saha, Atreyee Halder

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(30), P. 4467 - 4470

Published: Jan. 1, 2023

The developed methodology describes an environmentally benign protocol for electro-oxidative CF3-radical generation, followed by cascade cyclization fabricating isoxazoline scaffold from a β,γ-unsaturated oxime. Consecutive C-O and C-C bond formations were achieved through this method featuring mild, robust, scalable reaction conditions broad substrate scope. Mechanistic studies revealed the necessity of anodic oxidation process. Further conversion afforded other valuable derivatives.

Language: Английский

Citations

17
Visible light-mediated radical fluoromethylation via halogen atom transfer activation of fluoroiodomethane DOI Creative Commons
Patrick J. Deneny, Roopender Kumar, Matthew J. Gaunt

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(38), P. 12812 - 12818

Published: Jan. 1, 2021

Incorporation of the fluoromethyl group can profoundly influence physicochemical properties organic molecules, offering a promising strategy for discovery novel pharmaceutical agents. Direct fluoromethylation unfunctionalized C(sp

Language: Английский

Citations

38
Halotrifluoromethylation of 1,3-Enynes: Access to Tetrasubstituted Allenes DOI
Jinfeng Huang, Yimin Jia, Xiangyu Li

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(6), P. 2314 - 2319

Published: March 4, 2021

A highly regioselective copper-catalyzed 1,4-chloro- and bromotrifluoromethylation of 1,3-enynes has been presented for the first time, which affords an efficient transformation to access halo- CF3-containing tetrasubstituted allene derivatives with good excellent yield. This protocol is practical convenient, in a wide range functional groups are compatible. Applications this method gram-scale preparation late-stage functionalization biologically active molecules also demonstrated.

Language: Английский

Citations

33