New Reactions and Strategies in Synthesis

该研究的重点涉及合成化学新方法的开发，以及该方法在复杂合成问题中的后续应用。 这包括叔丁基二甲基甲硅烷基腙（TBSH）的化学发展，用于合成偕二卤化物，乙烯基卤化物，烃，重氮化合物，卤代TBSH，酯，醚和环丙烷衍生物，以及直接缩合反应形成混合吖嗪。 本研究计划研究混合吖嗪的新化学，目标是开发一种用于挤出氮以形成烯烃产物的催化方法。 新的方法直接和普遍的不对称合成季碳中心将被开发。 在相关工作中，还将寻求以立体控制方式建立邻位碳中心的方法。 本研究将探讨钯催化芳烃羧酸酯脱羧偶联反应及其延伸至质子脱羧反应及偶联反应。 收敛的，对映选择性的合成的细胞松弛素将实现适合于具有广泛变化的大环取代的类的成员的制备。 一个新的，名义上的芳香烃bicyclobenzenylene的合成将完成，并对这种理论上有趣的化学研究，迄今为止难以捉摸的分子。迈尔斯在哈佛大学化学和化学生物学系。 Myers博士将专注于开发可应用于复杂合成问题的合成方法。 这项工作在制药、农业和材料化学领域产生了更广泛的影响。 此外，该项目为研究生的培训提供了一个极好的环境。

The focus of this research involves the development of new methods in synthetic chemistry, and the subsequent application of the methodology to complex synthetic problems. This includes the development of the chemistry of tert-butyldimethylsilylhydrazones (TBSHs) for the synthesis of gem-dihalides, vinyl halides, hydrocarbons, diazo compounds, halogenated TBSHs, esters, ethers, and cyclopropane derivatives, and a directed condensation reaction to form mixed azines. Investigation to study new chemistry of mixed azines with the goal of developing a catalyzed process for the extrusion of dintrogen to form olefinic products is planned. Novel methodology directed toward a direct and generalizable enantioselective synthesis of quaternary carbon centers will be developed. In related work, a method for establishing vicinal carbon centers in a stereocontrolled manner will also be pursued. Studies to further develop a palladium-catalyzed decarboxylative coupling of arene carboxylates and its extension toward a protio-decarboxylation process as well as coupling reactions will be investigated. A convergent, enantioselective synthesis of the cytochalasins will be achieved suitable for the preparation of members of the class with widely variant macrocyclic substitution. A synthesis of the novel, nominally aromatic hydrocarbon bicyclopentadienylene will be completed and a study made of the chemistry of this theoretically interesting and thus far elusive molecule.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Andrew G. Myers in the Department of Chemistry and Chemical Biology at Harvard University. Dr. Myers will focus his work on developing synthetic methodology that can be applied to complex synthetic problems. The broader impact of the work is in the areas of pharmaceutical, agricultural and materials chemistry. Further, the project presents an excellent setting for the training of graduate students.