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.
