General Defluoroalkylation of Trifluoromethylarenes with Both Electron-Donating and -Withdrawing Alkenes.

Autor: Zhu M; Key Laboratory for Green Organic Synthesis and Application of Hunan Province, Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105, China., Wang QL; College of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China., Huang H; Key Laboratory for Green Organic Synthesis and Application of Hunan Province, Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105, China., Mao G; School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China., Deng GJ; Key Laboratory for Green Organic Synthesis and Application of Hunan Province, Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105, China.; School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China.
Jazyk: angličtina
Zdroj: The Journal of organic chemistry [J Org Chem] 2024 Sep 06; Vol. 89 (17), pp. 12591-12609. Date of Electronic Publication: 2024 Aug 14.
DOI: 10.1021/acs.joc.4c01531
Abstrakt: The incorporation of gem-difluoromethylene units into organic molecules remains a formidable challenge. Conventional methodologies for constructing aryldifluoromethyl derivatives relied on the use of high-functional fluorinating regents under harsh conditions. Herein, we report general and efficient photoredox catalytic systems for defluoroalkylation of readily available trifluoromethylarenes through selective C-F cleavage to deliver gem-difluoromethyl radicals which proceed through reductive addition to both electron-donating and withdrawing alkenes under transition-metal free conditions. Mechanistic studies reveal that thiol serves as both photocatalyst and HAT reagent under visible light irradiation. This synergistic photocatalysis and HAT catalysis protocol exhibits ample and salient features such as high chemo- and regioselectivity, broad substrate scope, amenable gram-scale synthesis and late-stage modification of bioactive molecules.
Databáze: MEDLINE
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