有机光氧化还原催化通过 1,5-氢转移自由基接力反应合成 δ-氟甲基化醇和胺。
Organic Photoredox-Catalyzed Synthesis of δ-Fluoromethylated Alcohols and Amines via 1,5-Hydrogen-Transfer Radical Relay.
机构信息
Engineering Technology Research Center of Henan Province for Photo- and Electrochemical Catalysis, College of Chemistry and Pharmaceutical Engineering , Nanyang Normal University , Nanyang 473061 , China.
College of Life Science & Bioengineering , Beijing University of Technology , Beijing 100124 , China.
出版信息
Org Lett. 2019 Jul 5;21(13):5116-5120. doi: 10.1021/acs.orglett.9b01714. Epub 2019 Jun 18.
The hydrotrifluoromethylation of benzyl-protected homoallylic alcohol and amine derivatives catalyzed by 2,4,5,6-tetra(9 H-carbazol-9-yl)isophthalonitrile (4CzIPN) was developed. This reaction delivered δ-fluoromethylated free alcohols and amines with in situ deprotection of benzyl protecting group under mild irradiation conditions. 4CzIPN was found to be a competent metal-free photoredox catalyst for activating several types of fluoromethylation reagents including CFSOCl, Togni's reagent, and 2-bromo-2,2-difluoroacetate via oxidative quenching and also CFSONa through reductive quenching to allow direct hydrotrifluoromethylation of simple alkenes and Michael acceptors.
2,4,5,6-四(9H-咔唑-9-基)间苯二甲腈(4CzIPN)催化苄基保护的偕烯丙醇和胺衍生物的氢三氟甲基化反应被开发出来。在温和的光照条件下，该反应可将 δ-氟甲基化的游离醇和胺进行原位脱苄基保护。研究发现，4CzIPN 是一种有效的无金属光氧化还原催化剂，可通过氧化猝灭作用激活多种类型的氟甲基化试剂，包括 CFSOCl、Togni 试剂和 2-溴-2,2-二氟乙酸酯，也可通过还原猝灭作用激活 CFSONa，从而实现简单烯烃和迈克尔受体的直接氢三氟甲基化。
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