Cargando…

Controllable Synthesis of Trifluoromethyl- or gem-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 (2a), 2-(nitromethylene)imidazolidine (2b), 2-cyanoimino-thiazolidine (2c), and (E)-1-methyl-2-nitroguanidine (2d), in a controlled manner, was developed. The hydroamination of α-(t...

Descripción completa

Detalles Bibliográficos
Autores principales: He, Jingjing, Sun, Zhudi, Deng, Yupian, Liu, Ying, Zheng, Pai, Cao, Song
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10145784/
https://www.ncbi.nlm.nih.gov/pubmed/37110766
http://dx.doi.org/10.3390/molecules28083530
_version_ 1785034420254670848
author He, Jingjing
Sun, Zhudi
Deng, Yupian
Liu, Ying
Zheng, Pai
Cao, Song
author_facet He, Jingjing
Sun, Zhudi
Deng, Yupian
Liu, Ying
Zheng, Pai
Cao, Song
author_sort He, Jingjing
collection PubMed
description A simple and straightforward addition or defluorination of α-(trifluoromethyl)styrenes with 2-nitroimino-imidazolidine (2a), 2-(nitromethylene)imidazolidine (2b), 2-cyanoimino-thiazolidine (2c), and (E)-1-methyl-2-nitroguanidine (2d), in a controlled manner, was developed. The hydroamination of α-(trifluoromethyl)styrenes with 2a, 2b, 2c, and 2d 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 2a and 2c 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.
format Online
Article
Text
id pubmed-10145784
institution National Center for Biotechnology Information
language English
publishDate 2023
publisher MDPI
record_format MEDLINE/PubMed
spelling pubmed-101457842023-04-29 Controllable Synthesis of Trifluoromethyl- or gem-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine He, Jingjing Sun, Zhudi Deng, Yupian Liu, Ying Zheng, Pai Cao, Song Molecules Article A simple and straightforward addition or defluorination of α-(trifluoromethyl)styrenes with 2-nitroimino-imidazolidine (2a), 2-(nitromethylene)imidazolidine (2b), 2-cyanoimino-thiazolidine (2c), and (E)-1-methyl-2-nitroguanidine (2d), in a controlled manner, was developed. The hydroamination of α-(trifluoromethyl)styrenes with 2a, 2b, 2c, and 2d 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 2a and 2c 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. MDPI 2023-04-17 /pmc/articles/PMC10145784/ /pubmed/37110766 http://dx.doi.org/10.3390/molecules28083530 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
He, Jingjing
Sun, Zhudi
Deng, Yupian
Liu, Ying
Zheng, Pai
Cao, Song
Controllable Synthesis of Trifluoromethyl- or gem-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine
title Controllable Synthesis of Trifluoromethyl- or gem-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine
title_full Controllable Synthesis of Trifluoromethyl- or gem-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine
title_fullStr Controllable Synthesis of Trifluoromethyl- or gem-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine
title_full_unstemmed Controllable Synthesis of Trifluoromethyl- or gem-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine
title_short Controllable Synthesis of Trifluoromethyl- or gem-Difluorovinyl-containing Analogues of Neonicotinoids by the Reaction of α-(Trifluoromethyl)styrenes with 2-Nitroimino-imidazolidine
title_sort controllable synthesis of trifluoromethyl- or gem-difluorovinyl-containing analogues of neonicotinoids by the reaction of α-(trifluoromethyl)styrenes with 2-nitroimino-imidazolidine
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10145784/
https://www.ncbi.nlm.nih.gov/pubmed/37110766
http://dx.doi.org/10.3390/molecules28083530
work_keys_str_mv AT hejingjing controllablesynthesisoftrifluoromethylorgemdifluorovinylcontaininganaloguesofneonicotinoidsbythereactionofatrifluoromethylstyreneswith2nitroiminoimidazolidine
AT sunzhudi controllablesynthesisoftrifluoromethylorgemdifluorovinylcontaininganaloguesofneonicotinoidsbythereactionofatrifluoromethylstyreneswith2nitroiminoimidazolidine
AT dengyupian controllablesynthesisoftrifluoromethylorgemdifluorovinylcontaininganaloguesofneonicotinoidsbythereactionofatrifluoromethylstyreneswith2nitroiminoimidazolidine
AT liuying controllablesynthesisoftrifluoromethylorgemdifluorovinylcontaininganaloguesofneonicotinoidsbythereactionofatrifluoromethylstyreneswith2nitroiminoimidazolidine
AT zhengpai controllablesynthesisoftrifluoromethylorgemdifluorovinylcontaininganaloguesofneonicotinoidsbythereactionofatrifluoromethylstyreneswith2nitroiminoimidazolidine
AT caosong controllablesynthesisoftrifluoromethylorgemdifluorovinylcontaininganaloguesofneonicotinoidsbythereactionofatrifluoromethylstyreneswith2nitroiminoimidazolidine