With support from the Organic Dynamics Program, Dr. Jackman will study solution structures of lithium enolates. The following sutides will be performed in connection with this project: (i) determination of the structures of the mixed aggregates of three lithium enolates with lithium perchlorate and lithium tetraphenylboride, (ii) NMR studies of dynamic processes in mixed aggregates, (iii) studies of the solvation of a series of substituted lithium phenolates, (iv) comprehen-sive analysis of the initial rates of C- and O-alkylation of lithioisobutyrophenone and lithio 2-isopropyl-alpha-tetralone by methyl tosylate in a variety of solvents with added lithium perchlorate and lithium tetraphenylboride, (v) studies of degenerate proton transfer with lithium phenolates, and (vi) design of enantioselective organolithium reagents. %%% Organolithium compounds provide the synthetic organic chemist with some of the most effective methods for controlling stereo- and regiochemistry in processes that involve formation of new carbon-carbon bonds. In the past, progress in this field has been severely hampered by lack of mechanistic understanding, which in turn is a consequence of lack of detailed knowledge of the precise structures that organolithium species adopt in solution. The proposed studies address the elucidation of solution structures and then seek to develop useful mechanistic concepts that are based upon these structures. The special effects of solvents and cosolvents upon the solution structure of organolithium species will be studied. In addition, new stereoselctive reagents that are based upon mixed aggregate formation will be explored.
