Zhang Xiaolong, Deng Jiahua, Ji Yong, Li Rong, Sivaguru Paramasivam, Song Qingmin, Karmakar Swastik, Bi Xihe
Department of Chemistry, Northeast Normal University, Changchun, 130024, China.
Department of Chemistry, Basirhat College, West Bengal State University, Basirhat, 743412, West Bengal, India.
Chemistry. 2023 Dec 1;29(67):e202302562. doi: 10.1002/chem.202302562. Epub 2023 Oct 19.
A silver-catalyzed regioselective defluorinative 1,3-dienylation of trifluoromethyl phenyl N-triftosylhydrazones using homoallenols as 1,3-dienyl sources provides a variety of α-(di)fluoro-β-vinyl allyl ketones with excellent functional group tolerance in moderate to good yields. The reaction proceeds through a silver carbene-initiated sequential etherification and Claisen type [3,3]-sigmatropic rearrangement cascade. The synthetic utility of this protocol was demonstrated through the downstream synthetic elaboration toward diverse synthetically useful building blocks.
以高烯丙醇为1,3 - 二烯源，通过银催化的三氟甲基苯基N-三氟甲磺酰腙的区域选择性脱氟1,3 - 二烯基化反应，可提供多种α-（二）氟-β-乙烯基烯丙基酮，具有优异的官能团耐受性，产率中等至良好。该反应通过银卡宾引发的连续醚化和克莱森型[3,3] - 西格玛重排级联反应进行。通过对各种合成有用的结构单元进行下游合成精细修饰，证明了该方法的合成实用性。
