We successfully demonstrated that Friedel−Crafts‐type allylation of phenol derivatives and allylic phosphates is catalyzed by the AgTFA/trimethylsilyl cyanide (Me₃SiCN) and Pd(OAc)₂/Me₃SiCN combined systems to afford the C‐allylated product in a highly regioselective manner. The corresponding silyl cyanometallates generated in situ are proposed to be the active catalytic species. Lewis acidity of the reversibly formed ion pairs is appropriately regulated for this reaction. The para‐allylated anisole and phenol derivatives are selectively obtained. The para‐substituted ones are converted to the ortho‐allylated products. The reactivity of the catalytic systems is strongly dependent on the electronic nature of both electrophile and nucleophile. Substitution of an aromatic ring on the allylic phosphate is essential for the reaction. Thus, the competitive reaction of a 1 : 1 mixture of cinnamyl and simple allyl phosphates affords only the cinnamyl‐substituted product.

中文翻译：

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原位生成的氰基硅烷金属硅酸盐催化的苯酚衍生物的Friedel-Crafts型烯丙基化

我们成功地证明了苯酚衍生物和烯丙基磷酸盐的弗里德尔-克拉夫茨型烯丙基化由AgTFA /氰化三甲基硅烷（ME催化₃的SiCN）和Pd（OAc）₂ / Me的₃的SiCN组合系统，得到Ç -allylated产物在高度区域选择性的方式。原位产生的相应的甲硅烷基氰基金属盐被认为是活性催化物质。可逆地形成的离子对的路易斯酸度对此反应进行适当调节。的对位被选择性地获得-allylated苯甲醚和苯酚衍生物。对位取代的被转换为邻位烯丙基化产品。催化体系的反应性在很大程度上取决于亲电试剂和亲核试剂的电子性质。芳基磷酸酯上芳环的取代对于反应是必不可少的。因此，肉桂酸和简单的烯丙基磷酸酯的1：1混合物的竞争性反应只能得到肉桂酸取代的产物。