Catalytic Methods for Stereoselective C-C Bond Formations

该项目的重点是建立新的合成方法，通过结合机理的见解和配体效应的系统检查，用于乙烯与乙烯基芳烃，1，3-二烯和应变烯烃的异二聚反应。还将探索最近发现的使用[X-Y]（X-Y，硅，锡和硼）试剂进行α，ω-二炔和联烯炔分子内环化的催化方法的新方面。由于X和Y基团作为相应的乙烯基或烯丙基衍生物引入产物中，因此反应后可官能化基团的数量增加。有待研究的概念性新想法包括：（a）使用不对称催化产生轴向手性1，3-二烯;（B）使用驻留的轴向手性来控制分子中其他地方的阻转选择性;和（c）轴向手性1，3-二烯的立体选择性反应。在合成复杂分子，如螺旋聚烯烃和高度官能化，轴向手性苯并环辛二烯的应用将被追求。有了这个奖项，有机和大分子化学计划是支持博士Thaliyil V. RajanBabu，化学系在俄亥俄州州立大学的研究。RajanBabu博士和他的学生正在开发有机化合物合成的选择性反应，从简单和丰富的原料，如乙烯，丙烯，丁二烯和苯乙烯开始。这些反应受催化量的过渡金属的影响，将简单的起始材料转化为更复杂的产物，为开发普遍适用于医药和工艺化学的高度控制的反应提供了希望。

This project is focused on the establishment of new synthetic methods, developed through a combination of mechanistic insights and a systematic examination of ligand effects, for the heterodimerization of ethylene with vinylarenes, 1,3-dienes and strained olefins. Novel aspects of recently discovered catalytic methods for intramolecular cyclization of alpha,omega-diynes and allenynes using [X-Y] (X-Y, silicon, tin and boron) reagents will also be explored. Since the X and Y groups are incorporated into the products as the respective vinyl or allyl derivatives, there is an increase in the number of functionalizable groups after the reaction. Conceptually new ideas to be investigated include: (a) generation of axially chiral 1,3-diene using asymmetric catalysis: (b) use of resident axial chirality to control atropselectivity elsewhere in a molecule; and (c) stereoselective reactions of axially chiral 1,3-dienes. Applications in the synthesis of complex molecules such as helical polyolefins and highly functionalized, axially chiral benzocyclooctadienes will be pursued.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Thaliyil V. RajanBabu, of the Department of Chemistry at Ohio State University. Dr. RajanBabu and his students are developing selective reactions for the synthesis of organic compounds, starting from simple and abundantly available feedstocks such as ethylene, propylene, butadiene and styrene. These reactions, effected by a catalytic amount of a transition metal, convert simple starting materials into more complex products, offering promise for the development of highly controlled reactions of general applicability to medicinal and process chemistry.