Donald James R, Berrell Sophie L
Department of Chemistry , University of York , Heslington , York , YO10 5DD , UK . Email:
Chem Sci. 2019 May 7;10(22):5832-5836. doi: 10.1039/c9sc01370a. eCollection 2019 Jun 14.
Herein, a novel methodology for radical cyanomethylation is described. The process is initiated by radical addition to the vinyl azide reagent 3-azido-2-methylbut-3-en-2-ol which triggers a cascade-fragmentation mechanism driven by the loss of dinitrogen and the stabilised 2-hydroxypropyl radical, ultimately effecting cyanomethylation. Cyanomethyl groups can be efficiently introduced into a range of substrates trapping of α-carbonyl, heterobenzylic, alkyl, sulfonyl and aryl radicals, generated from a variety of functional groups under both photoredox catalysis and non-catalytic conditions. The value of this approach is exemplified by the late-stage cyanomethylation of pharmaceuticals.
在此，描述了一种用于自由基氰甲基化的新方法。该过程由自由基加成到乙烯基叠氮试剂3-叠氮基-2-甲基丁-3-烯-2-醇引发，这触发了由氮气损失和稳定的2-羟丙基自由基驱动的级联碎片化机制，最终实现氰甲基化。氰甲基基团可以在光氧化还原催化和非催化条件下，通过捕获由各种官能团产生的α-羰基、杂苄基、烷基、磺酰基和芳基自由基，有效地引入到一系列底物中。该方法的价值通过药物的后期氰甲基化得到了例证。
