Chemo- and regioselective defluorinative annulation of (trifluoromethyl)alkenes with pyrazolones: synthesis and insecticidal activity of 6-fluoro-1,4-dihydropyrano[2,3-<i>c</i>]pyrazoles

Li, Chengxi; Li, Hengyuan; Yao, Guangkai; Liang, Xianghui; Zhao, Chen; Xu, Hanhong; Jiang, Huanfeng; Zhu, Chuanle

doi:10.1039/d2qo00786j

Cited by 10 publications

(5 citation statements)

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“…Zhu and co-workers reported the chemo-and regioselective defluorinative [3 + 3] annulation of trifluoromethyl alkenes with pyrazolones for the synthesis of dihydropyrano[2,3-c]pyrazoles (Scheme 7). [32] Using t-BuOLi as the base, only the addition of the carbon-based nucleophile to CF 3 -alkenes was observed while the intramolecular S N V reaction occurred at oxygen nucleophilic sites.…”

Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

Picking Two out of Three: Defluorinative Annulation of Trifluoromethyl Alkenes for the Synthesis of Monofluorinated Carbo‐ and Heterocycles

Ling,

Zhou

2024

The Chemical Record

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The increasing demand of organofluorine compounds in medicine, agriculture, and materials sciences makes sophisticated methods for their synthesis ever more necessary. Nowadays, not only the C−F bond formation but also the selective C−F bond cleavage of readily available poly‐ or perfluorine‐containing compounds have become powerful tools for the effective synthesis of organofluorine compounds. The defluorinative cross‐coupling of trifluoromethyl alkenes with various nucleophiles or radical precursors in an SN2’ manner is a convergent route to access gem‐difluoroalkenes, which in turn react with nucleophiles or radical precursors via an SNV‐type reaction. If the SNV reactions occur intramolecularly, the dual C−F bond cleavage of trifluoromethyl alkenes allows facile assembly of monofluorinated cyclic skeletons with structural complexity and diversity. In this personal account, we summarized the advances in this field on the basis of coupling and cyclization partners, including binucleophiles, alkynes, diradical precursors and radical precursors bearing a nucleophilic site. Accordingly, the annulation reactions can be achieved by base‐mediated sequential SN2′/SNV reactions, transition metal catalyzed or mediated reactions, photoredox catalysis, and the combination of photocatalytic reactions with SNV reaction. In the context of seminal works of others in this field, a concise summary of the contributions of the authors is also offered.

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Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

Picking Two out of Three: Defluorinative Annulation of Trifluoromethyl Alkenes for the Synthesis of Monofluorinated Carbo‐ and Heterocycles

Ling,

Zhou

2024

The Chemical Record

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“…The insecticidal activities against P. xylostella were investigated referring to previously reported methods. [26][27][28] A susceptible strain of P. xylostella was collected from South China Agricultural University, Guangzhou (N 23°8 0 , E 113°17 0 ), and the larvae were incubated in a glasshouse maintained 25 ± 1 °C and 65 ± 5% relative humidity (RH) under a photoperiod of 16 h:8 h (light/dark).…”

Section: Insecticidal Activitymentioning

confidence: 99%

Design, synthesis, insecticidal activities and translocation of amino acid–tralopyril conjugates as vectorizing agrochemicals

Yao

Han

Wen

et al. 2023

Pest Management Science

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BackgroundConjugating amino acid moieties to active ingredients has been recognized as an effective method for improving the precise targeting of the active form to the specific site. Based on the vectorization strategy, a series of amino acid–tralopyril conjugates were designed and synthesized as novel proinsecticide candidates, with the potential capability of root uptake and translocation to the foliage of crops.ResultsBioassay results showed excellent insecticidal activities of some conjugates, in particular, the conjugates 6b, 6e, and 7e, against the diamondback moth (Plutella xylostella), with equivalent insecticidal activity to chlorfenapyr (CFP). Importantly, conjugate 6e exhibited significantly higher in vivo insecticidal activity against P. xylostella than CFP. Furthermore, the systemic test experiments with Brassica chinensis demonstrated that conjugates 6e and 7e could be transported to the leaves, in contrast to CFP, which remained in the root.ConclusionThis study demonstrated the feasibility of amino acid fragment conjugation as a vectorization strategy for transporting non‐systemic insecticides into the leaves of B. chinensis while maintaining in vivo insecticidal activity. The findings also provide insights for subsequent mechanism studies on the uptake and transport of amino acid–insecticide conjugates in plants. © 2023 Society of Chemical Industry.

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“…Very recently, the chemo‐ and regioselective defluorinative [3+3] annulation of (trifluoromethyl)alkenes 68 with pyrazolones 1 has been reported to synthesize 6‐fluoro‐1,4‐dihydropyrano[2,3‐ c ]pyrazoles 69 (Scheme 68). [49] Among the bases used, t BuOLi was found as the optimum choice for this annulation reaction leading the targeted products 69 in high yields. Some of the synthesized 6‐fluoro‐1,4‐dihydropyrano[2,3‐ c ]pyrazole derivatives exhibited significant insecticidal activity (up to 100 %) against Plutella xylostella , which is a worldwide destructive pest.…”

Section: Ring Annulation Reactionsmentioning

confidence: 99%

“…Very recently, the chemo-and regioselective defluorinative [3 + 3] annulation of (trifluoromethyl)alkenes 68 with pyrazolones 1 has been reported to synthesize 6-fluoro-1,4dihydropyrano[2,3-c]pyrazoles 69 (Scheme 68). [49] Among the bases used, tBuOLi was found as the optimum choice for this annulation reaction leading the targeted products 69 in high yields. Some…”

Section: Ring Annulation Reactionsmentioning

confidence: 99%

C−H Functionalization Reactions of 1‐Aryl‐5‐pyrazolones

Purohit

Prajapati

et al. 2022

Eur J Org Chem

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In this contribution, we provide a comprehensive overview on the CÀ H activation/functionalization reactions of 1-aryl-5-pyrazolones, in particular, 1-aryl-3-methyl-1H-pyrazol-5(4H)-ones (edaravones) and their N-methyl analogues i. e., antipyrines covering the literature since 2013 (the year of the first report). This review summarizes the recent progress in CÀ H functionalization reactions of 1-aryl-5-pyrazolones including edaravone and antipyrine derivatives under transition-metal-catalyzed/free conditions and discusses the related mechanism according to the role of the catalytic species.

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Chemo- and regioselective defluorinative annulation of (trifluoromethyl)alkenes with pyrazolones: synthesis and insecticidal activity of 6-fluoro-1,4-dihydropyrano[2,3-c]pyrazoles

Abstract: The chemo- and regioselective defluorinative [3 + 3] annulation of (trifluoromethyl)alkenes and pyrazolones gives useful 6-fluoro-1,4-dihydropyrano[2,3-c]pyrazoles.

Cited by 10 publications

References 59 publications

Picking Two out of Three: Defluorinative Annulation of Trifluoromethyl Alkenes for the Synthesis of Monofluorinated Carbo‐ and Heterocycles

Picking Two out of Three: Defluorinative Annulation of Trifluoromethyl Alkenes for the Synthesis of Monofluorinated Carbo‐ and Heterocycles

Design, synthesis, insecticidal activities and translocation of amino acid–tralopyril conjugates as vectorizing agrochemicals

C−H Functionalization Reactions of 1‐Aryl‐5‐pyrazolones

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