Department of Chemistry, University of California , Berkeley, California 94720, United States.
Org Lett. 2016 Oct 21;18(20):5244-5247. doi: 10.1021/acs.orglett.6b02543. Epub 2016 Sep 30.
A method for the oxidative coupling of arylsilanes with nitrogen nucleophiles is reported. This method occurs with a broad range of heptamethyltrisiloxylarenes and nitrogen nucleophiles, proceeds with the arylsilane as limiting reagent, and does not require a fluoride activator with electron-poor arylsilanes. The combination of this method with C-H silylation generates arylamines from unactivated arenes with site selectivity controlled by steric effects. This combination of steps gives direct access to many compounds that cannot be accessed via alternative C-H functionalization methods, including direct C-H amination or the combination of C-H borylation and amination.
报道了一种芳基硅烷与氮亲核试剂的氧化偶联方法。该方法适用于多种七甲基三硅氧烷芳基硅烷和氮亲核试剂，以芳基硅烷为限制试剂，并且不需要用氟化物激活电子缺电子的芳基硅烷。该方法与 C-H 硅烷化反应相结合，可通过空间位阻效应控制的选择性，从未活化的芳基化合物中生成芳基胺。这些步骤的结合可以直接得到许多无法通过其他 C-H 官能化方法获得的化合物，包括直接 C-H 氨化或 C-H 硼化和氨化的组合。
