Exploiting the Reactivity of Dienes via Electrophilic Addition with Anionic and Radical Intermediates
Martinez, Jenny S.
MetadataShow full item record
Our group’s main focus has been to answer the question of direct functionalization at the γ-position of cycloalkanones. 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. Our group has set out to resolve this problem by examining stabilized dienolate intermediates in both anionic and radical conditions. These reactive intermediates have opened a wide array of product possibilities upon exposure to a series of diverse reaction partners. Through these methods, our group has managed to find conditions in which formation of new carbon–halogen bonds, carbon–oxygen and carbon–carbon bonds occurs selectively at the γ-position of enones and related systems. Additionally, the reactivity of dienes in pyrrole systems has also been studied. 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, along with gas-phase proton affinity studies of these compounds, has also accomplished.
Subjectorganic chemistry, chemistry, gamma functionalization, enones, heterocycles, pyridines, halogenation