Synthesis and Reactions of Strained Molecules and Polymers

这项研究将涉及合成一些含有严重扭曲的平面性的碳-碳双键的有机分子。这些扭曲使双键的化学和光谱性质发生了深刻的变化。将考察这些应变双键的结构(X射线结晶学)、应变能(计算)和反应性(动力学)，以了解烯烃键的机械扭曲如何转化为化学反应活性。分析还将包括扭曲的酰胺(准双键)，其结果可以提供关于肽键被酶水解的激活机制的洞察力。还计划在新的拓扑结构中合成含有双键的新的分子族。这些物种将能够评估双键对各种扭转和平面外弯曲的化学反应，从而有可能识别可能对特定分子扭曲特别敏感的烯烃反应流形。这项研究的第三部分利用高能、扭曲的烯烃作为单体来合成应变聚合物。这些反应使用复分解催化剂来实现聚合。描述了形成这些新型高能材料的新方法。有了这个奖项，有机合成计划将支持加州大学欧文分校的Kenneth J.Shea博士的研究。该研究探讨了结构变形对碳-碳双键和酰胺基团的反应活性的影响，该基团也可以被认为是准双键。应变聚合物也将由应变单体制成。这将产生新的方法和材料，应该有利于生物化学、医学以及化学工业的研究。

This research will involve the synthesis of a number of organic molecules that contain carbon-carbon double bonds severely twisted out of planarity. These distortions produce profound changes in both the chemical and spectroscopic properties of the double bond. The structure (x-ray crystallography), strain energy (computational) and reactivity (kinetics) of these strained double bonds will be examined in order to understand how mechanical distortions of the olefin linkage are translated into chemical reactivity. The analysis will also include distorted amides (quasi-double bonds), the results of which can provide insight regarding the mechanism of activation of the peptide bond towards hydrolysis by enzymes. The synthesis of new families of molecules containing the double bond in novel topologies is also planned. These species will enable the evaluation of the chemical response of the double bond to various torsions and out-of-plane bendings, leading to the possibility of identifying alkene reaction manifolds that may be particularly sensitive to specific molecular distortions. The third component of this research utilizes high-energy, twisted alkenes as monomers for the synthesis of strained polymers. The reactions employ metathesis catalysts to achieve polymerization. New methodology is described to form these novel, high energy materials. %%% With this award, the Organic Synthesis Program will support the research of Dr. Kenneth J. Shea at the University of California, Irvine. The research explores the influence of structural deformation on the reactivity of the carbon-carbon double bond and the amide group which may also considered a quasi-double bond. Strained polymers will also be made from strained monomers. This will generate new methodology and materials that should benefit research in biochemistry, medicine, as well as in the chemical industry.