Preparation and Some Subsequent Transformations of Tetraethynylmethane
Preparation and Some Subsequent Transformations of Tetraethynylmethane
复制标题
四乙炔甲烷的制备和后续转化
DOI：
10.1021/ja00099a020
复制
发表时间：
1994
影响因子：
15
通讯作者：
J. Bradshaw
中科院分区：
文献类型：
--
作者：
K. Feldman;Carolyn K. Weinreb;W. Youngs;J. Bradshaw
以二[（三甲基硅基）乙炔基]酮为原料，经10步反应合成了四乙炔基甲烷（1），总收率33%。这条路线的特点是（1）通过[3，3] σ转移的机构构建关键的中心四元中心和（2）在非常空间要求的环境中安装第四乙炔单元。替代路线和模型系统，这是更多的信息比生产力进行了讨论。最后，过渡金属介导的不稳定的1（及其衍生物）与不饱和配体的偶联提供了各种相对稳定的聚炔基化物质，这些物质可以无事件地被操纵。天然存在的碳同素异形体金刚石和石墨所表现出的广泛的期望的本体物理性质，包括几个“极端”，引起了人们对通过合理合成制备相关材料的强烈兴趣。1然而，由于聚合/表征困难，沿着限制了对广泛的结构上感兴趣的单体单元的访问
Tetraethynylmethane (1) was synthesized in 10 steps and 33% overall yield from bis [(trimethysilyl) ethynyl] ketone. This route features (1) construction of the critical central quaternarycenter via the agency of a [3, 3] sigmatropic shift and (2) installation of the fourth acetylene unit in a very sterically demanding environment. Alternative routes and model systems which were more informative than productive are also discussed. Finally, transition metal-mediated coupling of the rather unstable 1 (and derivatives) with unsaturated partners furnished a variety of relatively stable polylalkynylated species which could be manipulated without event.The broad range of desirable bulk physical properties, including several “extremes", exhibited by the naturally occurring carbon allotropes diamond and graphite have generated intense interest in preparing related materials by rational synthesis.* 1 However, limited access to a wide range of structurally interesting monomer units along with difficulties in polymerization/characterization