Transition-metal-free, direct C H radical trifluoromethylation of nitroimidazoles with Togni’s reagent

Wang, Hezhen; Wei, Chunyong; Zou, Haiyan; Linghu, Chengcheng; Wang, Zhiyuan; Wang, Jing; Chen, Yongzheng; Zhang, Lei

doi:10.1016/j.tetlet.2022.153659

Cited by 9 publications

(8 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Organic and organometallic photoredox catalysts have also been reported for the activation of Togni's reagents. Indeed, the Wang, Chen and Zhang group recently reported a metal‐free trifluoromethylation of nitroimidazoles with the Togni's reagent [235] and in 2014, the Scaiano group reported a metal‐free photoredox radical trifluoromethylation of heteroarenes under visible‐light irradiation using methylene blue as the organic photoredox catalyst in the presence of N , N , N’ , N’ ‐tetramethylethylenediamine, TMEDA, (Scheme 105, Equation (1)). Under light irradiation, methylene blue would first be semireduced by the amine, leading to the formation of a methylene blue radical that could then react with the Togni's reagent to generate a trifluoromethyl radical that would further lead to the formation of the trifluoromethylated product.…”

Section: Trifluoromethylation Of (Hetero)arenesmentioning

confidence: 99%

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

Baguia

Evano

2022

Chemistry A European J

View full text Add to dashboard Cite

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 and various methods have been developed for their synthesis. Among them, the direct perfluoroalkylation of C(sp 2 )À H bonds in (hetero)arenes is one of the most attractive and straightforward ones, provided that it proceeds with high levels of regioselectivity. In this review article, a comprehensive overview of advances in this field is presented, with a special focus on the reaction mechanisms involved in these transformations and their regioselectivity. All methods available have been classified according to the nature of the perfluoroalkyl chain introduced, trifluoromethylation reactions being overviewed in a separate section, and to the nature of the reagents/catalysts required.

show abstract

Section: Trifluoromethylation Of (Hetero)arenesmentioning

confidence: 99%

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

Baguia

Evano

2022

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…[114] Several examples of trifluoromethylation reactions at aromatic C(sp 2 )À H of aniline compounds or heterocyclic compounds have also been reported. [115][116][117][118][119] Trifluoromethylation at vinyl C(sp 2 )À H has also been reported. [120][121][122] For example, Xie and co-workers found that the reaction of N-morpholino-1-arylmethanine 62 with reagent 57 under electrolysis conditions yielded products 63 in which the C(sp 2 )À H bond of hydrazone 62 was trifluoromethylated (Scheme 24).…”

Section: Trifluoromethyl-and Trifluoromethylthiobenziodoxolesmentioning

confidence: 93%

“…Khaskin's group synthesized Ni(II) catalysts bearing trifluoromethyl groups and reported trifluoromethylation reactions of aromatic and heteroaromatic rings using a ligand‐free Ni catalysts and trifluoromethylbenziodoxole [114] . Several examples of trifluoromethylation reactions at aromatic C( sp 2 )−H of aniline compounds or heterocyclic compounds have also been reported [115–119] …”

Section: Trifluoromethyl‐ and Trifluoromethylthiobenziodoxolesmentioning

confidence: 99%

Recent Progress in Synthetic Applications of Cyclic Hypervalent Iodine(III) Reagents

2023

View full text Add to dashboard Cite

Hypervalent iodine compounds have found broad application in modern organic chemistry as reagents and catalysts. Cyclic hypervalent iodine reagents based on the benziodoxole heterocyclic system have higher stability compared to their acyclic analogues, which makes possible the preparation and safe handling of the reagents with special ligands such as azido, cyano, and trifluoromethyl groups. Numerous iodine‐substituted benziodoxole derivatives have been prepared and utilized as reagents for transfer of the substituent on hypervalent iodine to organic substrate. Reactions of these reagents with organic substrates can be performed under metal‐free conditions, in the presence of transition metal catalysts, or using photocatalysts under photoirradiation conditions. In this review, we focus on the most recent synthetic applications of cyclic hypervalent iodine(III) reagents with the following ligands: N3, NHR, CN, CF3, SCF3, OR, OAc, ONO2, and C(=N2)CO2R. The review covers literature published mainly in the last 5 years.magnified image

show abstract

“…Rather recently, Chen and Zhang et al . [ 32 ] reported the C—H trifluoromethylation reactions of nitroimidazoles 29 by employing Togni's reagent 2 as the reaction patterner. The reactions were run in the presence of KOAc in DMSO with white LED irradiation.…”

Section: Transition Metal‐free Trifluoromethylation Of Aromatic C(sp2...mentioning

confidence: 99%

Advances in the Transition Metal‐Free C—H Trifluoromethylation

2022

View full text Add to dashboard Cite

Trifluoromethyl group is one of the most frequently available and promising functional groups in pharmaceutical, agrochemical as well as material molecules. Developing synthetic methods for the synthesis of trifluoromethyl functionalized compounds by trifluoromethylation reactions occupies significant position in modern organic chemistry. On the other hand, as a typical tool of sustainable synthesis, transition metal-free synthesis possesses unique advantages in atom economy, easy product purification as well as excellent eco-tolerance. Consequently, transition metal-free trifluoromethylation reactions constitute the most important approaches for accessing trifluoromethylated molecules. Herein, the advances in the transition metalfree C-H trifluoromethylation reactions are reviewed for the first time. According to the updated state-of-art, both the catalytic reactions by conventional heating chemistry and the more sustainable photocatalysis are included, covering the trifluoromethylation reactions of C(sp 3 )-H bond, aromatic C(sp 2 )-H bond as well as the non-aromatic C(sp 2 )-H bond in different substrates over the last five years (2017-2021).

show abstract

Transition-metal-free, direct C H radical trifluoromethylation of nitroimidazoles with Togni’s reagent

Cited by 9 publications

References 35 publications

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

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

Recent Progress in Synthetic Applications of Cyclic Hypervalent Iodine(III) Reagents

Advances in the Transition Metal‐Free C—H Trifluoromethylation

Contact Info

Product

Resources

About