Synthesis and chemistry of homocubanes, bishomocubanes, and trishomocubanes
Synthesis and chemistry of homocubanes, bishomocubanes, and trishomocubanes
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高立方烷、二苯基立方烷和三苯基立方烷的合成和化学
DOI：
10.1021/cr00095a004
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发表时间：
1989
期刊：
影响因子：
62.1
通讯作者：
A. P. Marchand
中科院分区：
文献类型：
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作者：
A. P. Marchand
近年来，饱和多环“笼”分子对有机化学家产生了特殊的吸引力。除金刚烷外，大多数饱和笼状分子都含有相当大的应变能，因为它们(I)含有异常长的骨架碳-碳r键，(Ii)含有明显偏离109.5的异常ccc键角，(Iii)具有异常负的燃烧热，以及(Iv)与非应变体系相比具有异常正的生成热。通常，笼子分子中包含的应变能也通过不寻常的化学反应模式来表达。此外，这种应变能赋予笼状体系的热力学不稳定性是一个潜在的问题，合成化学家或有机化学家必须学会建设性地处理。
In recent years, saturated polycyclic “cage” molecules have held a special fascination for organic chemists. With the exception of adamantane, most saturated cage molecules contain considerable strain energy as evi-denced bythe factthat they (i) containunusually long framework carbon-carbon rr-bonds,(ii) contain unusual CCC bond angles that deviate significantly from 109.5,(iii) possess unusually negative heats of com-bustion, and (iv) possess unusually positive heats of formation when compared with nonstrained systems. Frequently, the strain energy contained within cage molecules also expresses itself throughunusual patterns of chemical reactivity. 1 Additionally, the thermody-namic instability that this strain energy confers upon cage systems is a potential problem that synthetic or-ganic chemists must learn to deal with constructively.