Abstract:
Herein, an Ir-catalyzed asymmetric allylic substitution reaction of methyl azaarenes is described. Azaarenes such as (benzo)thiazole, oxazole, benzoimidazole, pyridine, and (iso)quinoline are all tolerated. The corresponding chiral azaarene derivatives are obtained in good yields with high enantioselectivity (up to 96 % yield and 99 % ee). The utilization of the Knochel reagent TMPZnBr⋅LiBr warrants the in situ formation of benzylic nucleophiles without additional activating reagents. 1 H NMR studies suggested a two-fold function of the Knochel reagent in this reaction. The synthetic utility of this method has been showcased by a concise enantioselective synthesis of an allosteric protein kinase modulator.
摘要:
在这里,描述了甲基氮杂芳烃的Ir催化的不对称烯丙基取代反应。氮杂芳烃如(苯并)噻唑,恶唑,苯并咪唑,吡啶,和(异)喹啉都是耐受的。相应的手性氮杂芳烃衍生物以良好的产率和高对映选择性(高达96%产率和99%ee)获得。Knochel试剂TMPZnBr·LiBr的使用保证了在没有其他活化剂的情况下原位形成苄基亲核试剂。1HNMR研究表明Knochel试剂在该反应中具有双重功能。该方法的合成效用已通过变构蛋白激酶调节剂的简洁的对映选择性合成来展示。