Takagi Jun, Takahashi Kou, Ishiyama Tatsuo, Miyaura Norio
Division of Molecular Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan.
J Am Chem Soc. 2002 Jul 10;124(27):8001-6. doi: 10.1021/ja0202255.
The synthesis of 1-alkenylboronic acid pinacol esters via a palladium-catalyzed cross-coupling reaction of bis(pinacolato)diboron (pin(2)B(2), pin = Me(4)C(2)O(2)) with 1-alkenyl halides or triflates was carried out in toluene at 50 degrees C in the presence of KOPh (1.5 equiv) and PdCl(2)(PPh(3))(2)-2Ph(3)P (3 mol %). The borylation of acyclic and cyclic 1-alkenyl bromides and triflates was achieved in high yields with complete retention of configuration of the double bonds. The method was applied to the one-pot synthesis of unsymmetrical 1,3-dienes via the borylation-coupling sequence.
通过双(频哪醇)二硼(频哪醇硼烷，频哪醇 = 四甲基环丁二醇)与1-链烯基卤化物或三氟甲磺酸酯在钯催化下的交叉偶联反应合成1-链烯基硼酸频哪醇酯，反应在甲苯中于50℃、KOPh(1.5当量)和PdCl₂(PPh₃)₂ - 2Ph₃P(3摩尔%)存在的条件下进行。无环和环状1-链烯基溴化物及三氟甲磺酸酯的硼化反应以高收率实现，且双键构型完全保留。该方法应用于通过硼化 - 偶联序列一锅法合成不对称1,3 - 二烯。
