Spirocyclopropanated Bicyclopropylidenes: Straightforward Preparation, Physical Properties, and Chemical Transformations
作者:Armin de Meijere、Malte von Seebach、Stefan Zöllner、Sergei I. Kozhushkov、Vladimir N. Belov、Roland Boese、Thomas Haumann、Jordi Benet-Buchholz、Dmitrii S. Yufit、Judith A. K. Howard
DOI:10.1002/1521-3765(20010917)7:18<4021::aid-chem4021>3.0.co;2-e
日期:2001.9.17
"third-generation" perspirocyclopropanated dicyclopropylidenemethane 38 (21% yield). Mechanistic aspects of this and the other unusual reactions are discussed. The structures of all new unusual hydrocarbons were proven by X-ray crystal structure analyses, and the most interesting structural and crystal packing features are presented.
由7-环丙基二烯基螺[2.0.2.1]庚烷(4)(占总含量的24%)分三步制备全螺环丙烷化的双环亚丙基(6),或更有效的方法是,通过7,7-二溴[3] triangulane(15)的脱卤偶联反应( 82%)。事实证明,这种类型的还原性二聚反应可成功合成(E)-和(Z)-双(螺旋戊二烯)14(67%),甚至合成“第三代”螺环丙烷化的双环亚丙基17(从15占总17%) )。母体双环亚丙基1在180摄氏度下二聚生成[4]旋转烷,而130摄氏度在10 kbar压力下6发生二聚只是在打开一个三元环的情况下才产生聚螺环丙烷化(环亚丙基)环戊烷衍生物19(34 %,然后在高温下,聚螺环丙烷化的2-环亚丙基[3.2。2]丙炔衍生物20(25%产率)。全螺环丙烷化的双环亚丙基6和“第三代”双环亚丙基17不加重排就添加了溴,溴化氢和各种二卤卡宾。使用功能性取代的支链[7]三角烷28和支链二氯-C2v- [1