Progress toward the synthesis of apomorphine chiral auxiliary mediated interception of an intramolecularly formed N-acyl iminium ion /

by 1975- Nuckols, Michel Christian

Nuckols, Michel Christian. Progress Toward the Synthesis of Apomorphine: Chiral Auxiliary Mediated Interception of an Intramolecularly Formed N-Acyl Iminium Ion. (Under the direction of Daniel L. Comins.) Glaucine, which contains an aporphine skeleton, has been previously synthesized utilizing an intermolecular approach to form an iminium ion for the Pictet-Spengler reaction. A diastereomeric excess of 79% resulted as mediated by a chiral auxiliary. Progress was made in attempting to increase the diastereomeric excess by using an intramolecular approach to iminium ion formation. Apomorphine is a suitable platform on which to demonstrate the asymmetric interception of a chiral N-acyl iminium ion generated by intramolecular means. Several routes to this end were explored. These routes included the use of an intramolecular variant on the previously published work, Grubbs’ metathesis and Horner- Wadsworth-Emmons among others. While no route proved successful in the end, understanding of the formation of aporphine skeletons was expanded upon. Progress Toward the Synthesis of Apomorphine: Chiral Auxiliary Mediated Interception of an Intramolecularly Formed N-Acyl Iminium Ion by Michel Christian Nuckols A dissertation submitted to the Graduate faculty of North Carolina State University In partial fulfillment of the Requirements for the Degree of Doctor of Philosophy Chemistry Raleigh 2004 Approved by: Chair of Advisory Committee Daniel L. Comins Carl Bumgardner Suzanne Purrington James Whitesell