Metal Assisted Ionization in Carbenoids and Chiroptical Properties of Acyclic Dienes

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This grant in the Organic Dynamics Program supports research of Dr. Harry Walborsky, Florida State University, which is aimed at two areas of research in structural and mechanistic organic chemistry. The first investigation will provide information about the detailed pathway of the reaction of alkyllithiums with halogenated, saturated and unsaturated organic compounds. The second is aimed at a better understanding of methods for determing the structure of acyclic dienes. This project will investigate carbenoids, intermediates which possess a metal and a halogen on the same carbon atom. These intermediates may collapse to form carbenes or they may undergo ambiphilic reactions. The effect of variation in (1) metal (2) halogen and (3) nucleophile is to be studied. Since in the latter case, the metalating agent also serves as the nucleophile in a second step, mixed organolithiums will be used. A second part of the study will investigate chiroptical properties of acyclic dienes. For example, the 5-X- and 5-X-7-Y-adamantylideneacetaldehyde (and adamantylidenepropene) will be studied since the adamantyl system has a built-in reference which enables direct comparison of the effect of equatorial substituents X vs. Y on the pi-pi-star Cotton effects. The data so derived should allow configurational and conformational assignments to be made in otherwise undefined systems.