Catalytic Methods for Stereoselective C-C Bond Formations

本项目致力于建立乙烯与乙烯、1，3-二烯和张力烯烃的异二聚化反应的新的合成方法，通过机理的洞察和对配体效应的系统研究来开发。还将探索最近发现的使用[X-Y](X-Y)(X-Y，硅，锡和硼)试剂催化α，omega-diynes和allenynes分子内环化的新方法。由于X和Y基团分别作为乙烯基衍生物或烯丙基衍生物加入到产品中，因此反应后可官能化基团的数量增加。有待研究的新概念包括：(A)使用不对称催化生成轴手性1，3-二烯：(B)利用驻留轴手性来控制分子中其他位置的阿托品选择性；以及(C)轴手性1，3-二烯的立体选择性反应。将致力于复杂分子的合成，如螺旋聚烯烃和高度官能化的轴向手性苯并环辛二烯。获得该奖项后，有机和高分子化学计划将支持俄亥俄州立大学化学系的Thaliyil V.RajanBabu博士的研究。RajanBabu博士和他的学生正在开发用于合成有机化合物的选择性反应，从简单而丰富的原料开始，如乙烯、丙烯、丁二烯和苯乙烯。这些反应在一定量的过渡金属的催化作用下，将简单的起始原料转化为更复杂的产品，为开发广泛适用于药物和过程化学的高度受控的反应提供了希望。

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.