Mg-Prompted Polyfluoroarene C–H Functionalization: Formal Synthesis of Transfluthrin, Fenfluthrin, and Tefluthrin

Jia, Xuejiao; Wang, Junya; Duan, Xue; Yang, Jun; Li, Nan; Zhao, Na; Huang, Zhiyan

doi:10.1021/acs.joc.5b02022

Cited by 11 publications

(9 citation statements)

References 33 publications

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“…Reagents and solvents not listed and not specified were purchased from commercial suppliers. [11][12][13][14][15][16][17][18][19][20][21][22][23][24] However, since the synthesized compound contains small amount of impurities and the area integral in the 1 H NMR spectrum is substantially less than 0.5, it is difficult to accurately determine the content thereof. Because the synthesized compounds are all novel compounds, and the exact purity of the compound cannot be determined by the HPLC absorption peak, only rough values of the initial purity determined by NMR are given in the following compound data.…”

Section: Synthetic Proceduresmentioning

confidence: 99%

Synthesis, insecticidal activities and resistance in Aedes albopictus and cytotoxicity of novel dihaloacetylated heterocyclic pyrethroids

Zhu

Yang

Lao

et al. 2019

Pest Management Science

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BACKGROUND: The use of safe and effective insecticides against mosquito-borne stocks is still one of the most effective ways to rapidly interrupt the spread of diseases such as malaria, dengue etc., but many insects are resistant to most insecticides and most of the traditional pyrethroids (like permethrin, deltamethrin etc.) contain phenoxy groups so it is easy to form dibenzofuran, a pollutant, after photodegradation. It is therefore necessary to synthesize novel pyrethroids which have better mosquito-killing activity, poor resistance to mosquitoes, and no dibenzofuran formation during photodegradation. RESULTS: A series of novel dihaloacetylated heterocyclic pyrethroids were synthesized to enhance antimosquito activity. Bioassays based on the guidelines of the Chinese Center for Disease Control and Prevention (CDC) indicate that the synthesized compounds DCA-O (LC 50 = 2.95 ± 0.05 g L −1 ), DCA-01 (LC 50 = 5.83 ± 0.36 g L −1 ) and DCA-11 (LC 50 = 5.79 ± 1.51 g L −1 ) exhibit high insecticidal activities and sensitivity against Aedes albopictus while deltamethrin and permethrin produced moderate levels of resistance. Moreover, the analysis of the photodegradation implies that the novel compounds synthesized by substituting a phenoxy group with a heterocyclic ring do not form dibenzofuran, a pollutant. Lastly, the cytotoxicity data of pyrethroids on human dopaminergic neuroblastoma SH-SY5Y cells confirm that the synthesized compounds have low toxicity for the cells. CONCLUSION: Novel dihaloacetylated heterocyclic pyrethroids, made by simple synthesis steps, have better antimosquito activity, lower drug resistance, are less polluting to the environment and show low toxicity to human nerve cells. This also provides an effective idea for the synthesis of pyrethroids. Novel dihaloacetylated heterocyclic pyrethroids have better antimosquito activity, lower drug resistance, are less polluting to the environment, ahow low toxicity to human nerve cells and simple synthesis steps.

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Section: Synthetic Proceduresmentioning

confidence: 99%

Synthesis, insecticidal activities and resistance in Aedes albopictus and cytotoxicity of novel dihaloacetylated heterocyclic pyrethroids

Zhu

Yang

Lao

et al. 2019

Pest Management Science

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“…More recently, Lam and co‐workers [25] used a copper catalyst (Scheme 1 b ) and Gu and co‐workers [26] (Scheme 1 b ) used an N ‐heterocyclic carbene (NHC) organocatalyst to obtain fluorinated aryl carbinols using polyfluorophenyl trimethylsilane as a nucleophile for the addition to aldehydes. In 2015, Huang and co‐workers [27] (Scheme 1 c ) reported a Mg‐mediated polyfluoroaryl addition to aldehydes. Although some advancements in this field have been reported, these methods suffer from the requirement for highly flammable Grignard reagents, transition metals or NHC catalysts.…”

Section: Introductionmentioning

confidence: 99%

Transition Metal Catalyst‐Free, Base‐Promoted 1,2‐Additions of Polyfluorophenylboronates to Aldehydes and Ketones

et al. 2021

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An ovel protocol for the transition metal-free 1,2addition of polyfluoroaryl boronate esters to aldehydes and ketones is reported, which provides secondary alcohols,tertiary alcohols,a nd ketones.C ontrol experiments and DFT calculations indicate that both the ortho-F substituents on the polyfluorophenyl boronates and the counterion K + in the carbonate base are critical. The distinguishing features of this procedure include the employment of commercially available starting materials and the broad scope of the reaction with aw ide variety of carbonyl compounds giving moderate to excellent yields.I ntriguing structural features involving O À H•••O and O À H•••N hydrogen bonding,a sw ell as areneperfluoroarene interactions,inthis series of racemic polyfluoroaryl carbinols have also been addressed.

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“…Substituted quinolines can be synthesized by using classic cyclization reactions such as Doebner–von Miller, Combes, Conrad–Limpach–Knorr, Friedlander syntheses, and others, − whereas aryl(quinolin-4-yl)methanols can be prepared through the reaction of quinoline-4-carboxaldehydes with aromatic organometallic reagents; − quinolines bearing different functional groups at the C4 position are more commonly accessed from halogenated substrates by exploiting the reactivity of the corresponding lithium, − magnesium, and zinc organometallic intermediates. For example, Mongin and co-workers have explored a Br/Mg exchange reaction promoted by a tributylmagnesium ate complex to prepare 4-substituted quinolines. , …”

Section: Introductionmentioning

confidence: 99%

Synthesis of 7-Chloroquinoline Derivatives Using Mixed Lithium-Magnesium Reagents

et al. 2021

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We have prepared a library of functionalized quinolines through the magnesiation of 7-chloroquinolines under mild conditions, employing both batch and continuous flow conditions. The preparation involved the generation of mixed lithium-magnesium intermediates, which were reacted with different electrophiles. Mixed lithium-zinc reagents allowed the synthesis of halogenated and arylated derivatives. Some of the synthesized 4-carbinol quinolines have shown interesting antiproliferative properties, their hydroxyl group being a suitable amino group bioisostere. We also report a two-step approach for optically active derivatives.

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Mg-Prompted Polyfluoroarene C–H Functionalization: Formal Synthesis of Transfluthrin, Fenfluthrin, and Tefluthrin

Cited by 11 publications

References 33 publications

Synthesis, insecticidal activities and resistance in Aedes albopictus and cytotoxicity of novel dihaloacetylated heterocyclic pyrethroids

Synthesis, insecticidal activities and resistance in Aedes albopictus and cytotoxicity of novel dihaloacetylated heterocyclic pyrethroids

Transition Metal Catalyst‐Free, Base‐Promoted 1,2‐Additions of Polyfluorophenylboronates to Aldehydes and Ketones

Synthesis of 7-Chloroquinoline Derivatives Using Mixed Lithium-Magnesium Reagents

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