Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Flemingovo nam., 2, 166 10, Prague 6, Czech Republic.
Department of Organic Chemistry, Faculty of Science, Charles University, Hlavova 2030/8, 128 43 Prague, Czech Republic.
J Org Chem. 2020 Sep 4;85(17):11482-11489. doi: 10.1021/acs.joc.0c01610. Epub 2020 Aug 19.
A straightforward synthesis of 1-azido-2-bromo-1,1,2,2-tetrafluoroethane on a multigram scale from 1,2-dibromotetrafluoroethane and sodium azide in a novel process initiated by organomagnesium compounds (-PrMgCl·LiCl, turbo Grignard) is reported. Synthetic utility of the title azide in the preparation of N-tetrafluoroethylated and N-difluoromethylated five-membered nitrogen heterocycles was demonstrated with azide-alkyne cycloaddition to -bromotetrafluoroethyl 1,2,3-triazoles, subsequent reduction to -tetrafluoroethyl triazoles, rhodium-catalyzed transannulation with nitriles to N-tetrafluoroethylated imidazoles and rhodium-catalyzed ring-opening, and cyclization to N-difluoromethylated oxazoles and thiazoles.
本文报道了一种从 1,2-二溴四氟乙烷和叠氮化钠出发，通过有机镁化合物（-PrMgCl·LiCl、涡轮格氏试剂）引发的新型反应，以克级规模直接合成 1-叠氮基-2-溴-1,1,2,2-四氟乙烷的方法。标题叠氮化物在制备 N-全氟乙基化和 N-二氟甲基化五元氮杂环中的合成用途通过叠氮化物-炔烃环加成反应得到-溴代四氟乙基 1,2,3-三唑，随后还原得到-N-全氟乙基三唑，与腈的铑催化反芳烃化得到 N-全氟乙基咪唑以及铑催化开环和环化得到 N-二氟甲基化恶唑和噻唑得到了证明。
