The Electronic Factor in Face Selection

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This grant from the Organic Dynamics Program supports the work of Professor William J. le Noble at the State University of New York at Stony Brook to study the electronic origins of pi- diastereofacial selectivity by using various substituted adamantan-2-ones and related compounds. The specific projects are: (1) addition reactions, including dihydroxylation, Grob fragmentation, Michael addition, and Claisen rearrangement; (2) studies directed to differentiate between the theoretical models of Ahn, Cieplak, and Felkin; (3) changes in skeleton and substitution patterns by expanding/reducing adamantane by one methylene unit at C6, by studying more powerful 5-substituent effects (N-oxides and boron and ammonium compounds), by studying the 4,9-disubstitution effect, by studying the 5,7-disubstitution effect, and by modifying the trigonal center at C2. %%% In this project Professor William K. le Noble will study the electronic effects that govern pi-diastereofacial selectivities in bond making (and breaking) to (and from) ketones, imines, and olefins. The adamantane frame is selected to eliminate interfering steric and conformational effects. The study concentrates on standard addition reaction, differentiating between theoretical models, and will explore the influence of powerful substituents and structural rigidity.