Controllable Synthesis of Trifluoromethyl- or <i>gem</i>-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine
A simple and straightforward addition or defluorination of α-(trifluoromethyl)styrenes with 2-nitroimino-imidazolidine (<b>2a</b>), 2-(nitromethylene)imidazolidine (<b>2b</b>), 2-cyanoimino-thiazolidine (<b>2c</b>), and (<i>E</i>)-1-methyl-2-nitroguani...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-04-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/8/3530 |
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| author | Jingjing He Zhudi Sun Yupian Deng Ying Liu Pai Zheng Song Cao |
| author_facet | Jingjing He Zhudi Sun Yupian Deng Ying Liu Pai Zheng Song Cao |
| author_sort | Jingjing He |
| collection | DOAJ |
| description | A simple and straightforward addition or defluorination of α-(trifluoromethyl)styrenes with 2-nitroimino-imidazolidine (<b>2a</b>), 2-(nitromethylene)imidazolidine (<b>2b</b>), 2-cyanoimino-thiazolidine (<b>2c</b>), and (<i>E</i>)-1-methyl-2-nitroguanidine (<b>2d</b>), in a controlled manner, was developed. The hydroamination of α-(trifluoromethyl)styrenes with <b>2a</b>, <b>2b</b>, <b>2c</b>, and <b>2d</b> was completed in the presence of DBN at room temperature within 0.5–6 h, affording structurally diverse β-trifluoromethyl-β-arylethyl analogues of neonicotinoids in moderate to good yields. The γ,γ-difluoro-β-arylallyl analogues of neonicotinoids were also successfully synthesized via defluorination of α-(trifluoromethyl)styrenes, with <b>2a</b> and <b>2c</b> using NaH as base at an elevated temperature together with a prolonged reaction time of 12 h. The method features simple reaction setup, mild reaction conditions, broad substrate scope, high functional group compatibility, and easy scalability. |
| first_indexed | 2024-03-11T04:41:52Z |
| format | Article |
| id | doaj.art-b77d81cfa031426498795313b416e320 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T04:41:52Z |
| publishDate | 2023-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-b77d81cfa031426498795313b416e3202023-11-17T20:40:21ZengMDPI AGMolecules1420-30492023-04-01288353010.3390/molecules28083530Controllable Synthesis of Trifluoromethyl- or <i>gem</i>-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidineJingjing He0Zhudi Sun1Yupian Deng2Ying Liu3Pai Zheng4Song Cao5Shanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology (ECUST), Shanghai 200237, ChinaShanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology (ECUST), Shanghai 200237, ChinaShanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology (ECUST), Shanghai 200237, ChinaShanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology (ECUST), Shanghai 200237, ChinaShanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology (ECUST), Shanghai 200237, ChinaShanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology (ECUST), Shanghai 200237, ChinaA simple and straightforward addition or defluorination of α-(trifluoromethyl)styrenes with 2-nitroimino-imidazolidine (<b>2a</b>), 2-(nitromethylene)imidazolidine (<b>2b</b>), 2-cyanoimino-thiazolidine (<b>2c</b>), and (<i>E</i>)-1-methyl-2-nitroguanidine (<b>2d</b>), in a controlled manner, was developed. The hydroamination of α-(trifluoromethyl)styrenes with <b>2a</b>, <b>2b</b>, <b>2c</b>, and <b>2d</b> was completed in the presence of DBN at room temperature within 0.5–6 h, affording structurally diverse β-trifluoromethyl-β-arylethyl analogues of neonicotinoids in moderate to good yields. The γ,γ-difluoro-β-arylallyl analogues of neonicotinoids were also successfully synthesized via defluorination of α-(trifluoromethyl)styrenes, with <b>2a</b> and <b>2c</b> using NaH as base at an elevated temperature together with a prolonged reaction time of 12 h. The method features simple reaction setup, mild reaction conditions, broad substrate scope, high functional group compatibility, and easy scalability.https://www.mdpi.com/1420-3049/28/8/3530α-(trifluoromethyl)styrenes2-nitroimino-imidazolidinetrifluoromethyl- or <i>gem</i>-difluorovinyl-containing analogues of neonicotinoids |
| spellingShingle | Jingjing He Zhudi Sun Yupian Deng Ying Liu Pai Zheng Song Cao Controllable Synthesis of Trifluoromethyl- or <i>gem</i>-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine Molecules α-(trifluoromethyl)styrenes 2-nitroimino-imidazolidine trifluoromethyl- or <i>gem</i>-difluorovinyl-containing analogues of neonicotinoids |
| title | Controllable Synthesis of Trifluoromethyl- or <i>gem</i>-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine |
| title_full | Controllable Synthesis of Trifluoromethyl- or <i>gem</i>-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine |
| title_fullStr | Controllable Synthesis of Trifluoromethyl- or <i>gem</i>-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine |
| title_full_unstemmed | Controllable Synthesis of Trifluoromethyl- or <i>gem</i>-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine |
| title_short | Controllable Synthesis of Trifluoromethyl- or <i>gem</i>-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine |
| title_sort | controllable synthesis of trifluoromethyl or i gem i difluorovinyl containing analogues of neonicotinoids by the reaction of α trifluoromethyl styrenes with 2 nitroimino imidazolidine |
| topic | α-(trifluoromethyl)styrenes 2-nitroimino-imidazolidine trifluoromethyl- or <i>gem</i>-difluorovinyl-containing analogues of neonicotinoids |
| url | https://www.mdpi.com/1420-3049/28/8/3530 |
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