New Reactions and Strategies in Synthesis

这项研究的重点涉及合成化学中新方法的开发，以及随后该方法在复杂合成问题中的应用。这包括用于合成宝石二卤化物、乙烯基卤化物、碳氢化合物、重氮化合物、卤代叔丁基二甲基硅肼(TBSHs)、酯、醚和环丙烷衍生物的叔丁基二甲基硅肼(TBSHs)的化学开发，以及用于合成混合叠氮的定向缩合反应。计划研究混合氮杂的新化学，目标是开发一种催化过程，使丁香酮挤出生成烯烃产品。将开发一种新的方法，旨在直接和普遍地合成季碳中心的对映选择性合成。在相关工作中，还将寻求以立体控制的方式建立邻近碳中心的方法。进一步开发钯催化的芳烃羧酸盐的脱羧基偶联反应及其向原脱羧基过程的扩展以及偶联反应的研究将被研究。细胞松弛素的收敛、对映体选择性的合成将适用于制备具有广泛变异的大环取代的一类成员。一项新的、名义上是芳烃双环戊二烯的合成将完成，并将对这种理论上有趣但迄今难以捉摸的分子的化学进行研究。有了这个奖项，有机化学和高分子化学计划将支持哈佛大学化学和化学生物学系安德鲁·G·迈尔斯博士的研究。迈尔斯博士将把工作重点放在开发可应用于复杂合成问题的合成方法上。这项工作的更广泛影响是在制药、农业和材料化学领域。此外，该项目为研究生的培训提供了一个很好的环境。

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.