Feb 28
Chemistry Department Seminar: Jenny Martinez (Yale)
To this day, countless chemical transformations are known for the functionalization of the α- and β-positions of cyclic ketones. However, few methods are known for functionalization at the γ-position of cycloalkanes. To answer the question of direct functionalization at the γ-position of cycloalkanones, stabilized dienolate intermediates in both anionic and radical conditions have been extensively studied. These reactive intermediates have opened a wide array of product possibilities upon exposure to a series of diverse reaction partners. Through these methods, reaction conditions have been discovered for the formation of new carbon–halogen bonds, carbon–oxygen and carbon–carbon bonds selectively at the γ-position of enones and related systems. Additionally, the reactivity of dienes in pyrrole systems has also been examined. As a result, a protocol to access new sterically demanding halopyridines via the Ciamician–Dennstedt rearrangement has been discovered. Furthermore, an economical and efficient synthesis of 2,6-di-t-butylpyridine analogues was also accomplished.