Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan.
Org Lett. 2020 Jul 17;22(14):5540-5544. doi: 10.1021/acs.orglett.0c01904. Epub 2020 Jul 7.
Regioselective difunctionalization of 2,6-difluorophenols with aryl sulfoxides and nucleophiles has been accomplished. The reaction is composed of (1) Pummerer-based [3,3] sigmatropic dearomatization to generate 2,4-cyclohexadienone, (2) Michael addition of a nucleophile, and (3) liberation of HF for rearomatization. Besides the [3,3] rearrangement, [2,3] sigmatropic rearrangement from sulfonium ylide generated from alkyl sulfoxide promotes the dearomatization, resulting in installation of α-sulfanylalkyl group.
芳基砜和亲核试剂对 2,6-二氟苯酚的区域选择性双官能化已完成。该反应由（1）基于 Pummerer 的[3,3]σ重排生成 2,4-环己二烯酮，（2）亲核试剂的迈克尔加成，和（3）HF 的释放进行再芳构化组成。除了[3,3]重排，烷基砜生成的叶立德的[2,3]σ重排也促进了去芳构化，导致α-硫烷基烷基的安装。
