Rhodium-catalyzed formal [4 + 3] annulation reaction of N-methoxybenzamides with gem‑difluorocyclopropenes: A combination of experimental and theoretical studies

He, Yimiao; Tian, Limei; Chang, Xuexue; Qu, Zeming; Huang, Yanmin; Huang, Chusheng; Sun, Qing; Wang, Honggen

doi:10.1016/j.cclet.2022.01.068

Cited by 20 publications

(4 citation statements)

References 57 publications

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“…Regioselective 1,2-migratory insertion of fluorovinyl tosylate then gives a metallacycle intermediate IV . Subsequent β-F elimination 22 forms intermediate V and releases the catalyst. In subsequent Michael addition/elimination reactions, the desired product 3 is generated (X = H).…”

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confidence: 99%

CpIr(iii) and CpRh(iii)-catalyzed annulation of salicylaldehydes with fluorinated vinyl tosylates

Zhao

Cai

et al. 2022

Chem. Commun.

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confidence: 99%

CpIr(iii) and CpRh(iii)-catalyzed annulation of salicylaldehydes with fluorinated vinyl tosylates

Zhao

Cai

et al. 2022

Chem. Commun.

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“…2021 年, 周志和易伟课题组 [22] 发展了 Cp*Rh III 催化的 N-甲氧基苯酰胺苯环上 C-H 键活化与二氟环丙烯的[4＋3]环加成反应(图 2a). 几乎同时, 王洪根课题组、贺益苗课题组以及孙青课题组 [23] 联合报道化学学报同年, 吴勇课题组 [24] 报道了在金属铑催化下, 含氮杂环, 芳基取代的二氟环丙烯以及水三组分反应得到相应的含氮杂环化合物 2022 年, 范学森与张新迎课题组 [25] 开发了一种有效的方法来构建吡啶并嘧啶酮骨架化合物(图 6). Rh-catalyzed annulation of 1-arylpyrazolidinones with difluorocyclopropenes giving fluorinated pyridopyrimidinone derivatives 最近, 姜波课题组 [26] 环加成方式形成五元杂环 [31] .…”

Section: 过渡金属催化的含导向基 C-h 键活化环化反应unclassified

Recent Advances in the Transformation of Difluorocyclopropenes^★

Jiapian,

Fei,

Jie

2023

Acta Chimica Sinica

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In recent years, organic reactions involving difluorocyclopropenes have attracted the attention of organic chemists and have made great progress. The reactions mainly include: (1) cyclization: a) transition-metal catalyzed C-H bond activation cyclization with directing groups; b) cyclization reactions with non-directing groups; (2) hydrogenation reduction; (3) fluorination as "F" source reagents. In this paper, the synthesis methods and applications of difluorocyclopropenes in past 10 years are summarized. The conversion reactions of difluorocyclopropenes are emphasized. Additionally, difluorocyclopropenes have aroused considerable interests both from a structural standpoint and their participation in various ring-opening reactions. Given the increasing application of cyclopropyl skeleton in the development of drugs and unarguable importance of fluorinated compounds in medicinal chemistry and agrochemistry, it is no doubt that difluorocyclopropenes are encountered into bioactive molecular and at present lie among "emerging fluorinated motifs". Although the synthesis and application of structurally diverse difluorocyclopropenes have been witnessed in the past decade, the most widely used methods for the preparation of these compounds include difluoromethylenation of alkynes and difluoromethylation of heteroatom nucleophiles (such as NaF, NaI, n BuN4X, etc.) with a difluorocarbene reagent, which can be generated from various precursors (such as TMSCF3, TMSCF2X, Ph3P ＋ CF2CO2 -, TFDA, etc.). For the transition metal-catalyzed cyclization of difluorocyclopropenes, some common metal salts (such as rhodium, ruthenium, copper, palladium, silver) are used as catalysts. Moreover, the metallic hydrogen (M-H) reduction strategy is a simple and efficient method for the hydrogenation reduction of difluorocyclopropenes leading to difluorocyclopropanes, and the asymmetric hydrogenation reduction of difluorocyclopropenes can be achieved in the presence of chiral ligands. In fluorination reactions, difluorocyclopropenes have some advantages that cannot be achieved by traditional fluorination reagents for the direct fluorination and functionalization of hydroxyl groups (such as fluorination of polyhydroxyl alcohols). Of course, the biggest disadvantage of difluorocyclopropene as a fluorine source lies in its poor atomic economy, which has been criticized. Despite the remarkable achievements in the reactions of difluorocyclopropenes, there are still many issues that need to be addressed. For instance, difluorocyclopropenes are rarely applied in traditional radical reactions, photocatalysis, electrocatalysis and flow chemistry. Hopefully, difluorocyclopropenes can gradually appear in photo-and electro-catalyzed radical chemistry, and the related asymmetric reactions will also get more attention and development in the near future.

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“…Two promising pathways have emerged in this field. The first approach involves migratory insertion of a transition metal followed by β-fluorine elimination of polyfluorinated molecules, which has been extensively explored and developed . The second pathway involves transition-metal-catalyzed oxidative C–F bond addition, facing challenges due to the high bond energy …”

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Palladium-Catalyzed Diversified Synthesis of Monofluorinated Alkenes from Allylic gem-Difluorides through Pd–OH Intermediate

Tang,

Liu,

et al. 2023

Org. Lett.

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Rhodium-catalyzed formal [4 + 3] annulation reaction of N-methoxybenzamides with gem‑difluorocyclopropenes: A combination of experimental and theoretical studies

Cited by 20 publications

References 57 publications

CpIr(iii) and CpRh(iii)-catalyzed annulation of salicylaldehydes with fluorinated vinyl tosylates

CpIr(iii) and CpRh(iii)-catalyzed annulation of salicylaldehydes with fluorinated vinyl tosylates

Recent Advances in the Transformation of Difluorocyclopropenes^★

Palladium-Catalyzed Diversified Synthesis of Monofluorinated Alkenes from Allylic gem-Difluorides through Pd–OH Intermediate

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Rhodium-catalyzed formal [4 + 3] annulation reaction of N-methoxybenzamides with gem‑difluorocyclopropenes: A combination of experimental and theoretical studies

Cited by 20 publications

References 57 publications

Cp*Ir(iii) and Cp*Rh(iii)-catalyzed annulation of salicylaldehydes with fluorinated vinyl tosylates

Cp*Ir(iii) and Cp*Rh(iii)-catalyzed annulation of salicylaldehydes with fluorinated vinyl tosylates

Recent Advances in the Transformation of Difluorocyclopropenes★

Palladium-Catalyzed Diversified Synthesis of Monofluorinated Alkenes from Allylic gem-Difluorides through Pd–OH Intermediate

Contact Info

Product

Resources

About

CpIr(iii) and CpRh(iii)-catalyzed annulation of salicylaldehydes with fluorinated vinyl tosylates

CpIr(iii) and CpRh(iii)-catalyzed annulation of salicylaldehydes with fluorinated vinyl tosylates

Recent Advances in the Transformation of Difluorocyclopropenes^★