Synthesis and Reactions of Strained Molecules and Polymers

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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.