Chapter I: Studies of the Catalytic Mukaiyama Aldol Reactions of Trimethylsilyoxyfuran Chapter II: The Synthesis of a Photoaffinity Probe for a Caloric Restriction Mimic

Chapter I: Studies of the Catalytic Mukaiyama Aldol Reactions of Trimethylsilyoxyfuran;The Applicability of the Corey-Bakshi-Shibata reagent as an asymmetric catalyst for Mukaiyama type aldol reactions was further evaluated and the scope extended. The catalyst loading was examined and it was found that it could be reduced from 48 mol% to ∼10 mol%. The catalytic cycle was examined and the critical variables controlling enantioselectivity and diastereoselectivity identified. The tolerance of the critical reaction variables to changes was determined.;Chapter II: The Synthesis of a Photoaffinity Probe for a Caloric Restriction Mimic;The synthesis of a new photoaffinity probe containing a diazarine ring is described. The synthesis takes advantage of a Wittig reaction as well as a Michael-Dieckmann annulation to synthesize a triketone core which is believed to be important in binding to the cellular target mediating the processes resulting in the observed mimesis of caloric restriction.