Fenestrane Approach Toward Planar Tetracoordinate Carbon

一系列应变分子合成的研究， 在本研究中称为"fenestrane和/或fenestrene" 将提高对这种粘合特性的理解， 化合物. 12 π轮烯的合成与研究 （正戊烷-1，3，5，7，9，11-六烯）和14 pi-<$5.5.6.6.! 就键合而言，窗烷七烯是重要的 碳的特性。 在走向"平面化"的过程中， 四面体碳，目标已被选择提供 键角变形/应变能逐渐增加， 比较的目的。 初步研究将集中在 5.5.5.5! fenestranes，（tccc）and（tctc），as 5.5.6.6!芬雌烯。 从综合中获得的知识 上述分子将被用于研究 反应性越大<$5.5.5.5!芬雌烯。 此外，本发明还提供了一种方法， 对窗烷轮烯合成的研究将 帮助确定休克尔π-离域化是否在 这种多醌轮烯稳定性;这些轮烯 主要由稠合的五元环组成。 各种复杂程度的计算 这些窗烷提供了精确的键长， 键角与X射线结构的比较是可能的， 在应变中没有实验热化学数据， 系统的准确性评估的计算 方法. 目标的化学/反应性研究 分子将提供急需的洞察的性质， 有机分子中的碳化学键， 特别是关于碳原子，其中应变和 角度变形可以影响杂化的变化。 有机合成计划正在支持 James M.的研究。厨师. 该研究将提供 更好地理解应变对碳的影响， 通过构建具有高度 扭曲的结构。 这有可能提供更深层次的 深入了解化学反应性如何能够有效地 被操纵了

The study of the synthesis of a number of strained molecules, termed "fenestranes and/or fenestrenes" in this investigation will improve the understanding of the bonding character in such compounds. The synthesis and study of the 12 pi annulene (staurane-1,3,5,7,9,11-hexaene) and the 14 pi-ı5.5.6.6.! fenestrane heptaene are important in terms of the bonding character of carbon. In the approach toward "planarization" of tetrahedral carbon, the targets have been chosen to provide a gradual increase in bond angle deformation/strain energy for purposes of comparision. Initial research will focus on the synthesis of the ı5.5.5.5!fenestranes, (tccc) and (tctc), as well as ı5.5.6.6!fenestrenes. Knowledge gained from synthesis of the above molecules will then be employed for the study of the more reactive ı5.5.5.5!fenestrenes. In addition, investigation of the synthesis of fenestrane annulenes will help to determine if Huckel pi-delocalization plays a role in the stability of such polyquinene annulenes; these annulenes are primarily composed of fused five-membered rings. Calculations at various levels of sophistication for a variety of these fenestranes have provided accurate bond lengths and bond angles where comparison with X-ray structures is possible, there are no experimental thermochemical data in strained systems for evaluation of the accuracy of the computational methods. Studies of the chemistry/reactivity of the target molecules will provide much needed insight into the nature of the carbon chemical bond in organic molecules in general, and in particular with respect to carbon atoms where strain and angle deformation may effect a change in hybridization. The Organic Synthesis Program is supporting the continuation of the studies of Dr. James M. Cook. The research will provide greater understanding of the effect of strain upon the carbon framework by the construction of molecules which have highly distorted structures. This has the potential to provide deeper insight into how chemical reactivity can be usefully manipulated.