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Synthesis of Adamantane Derivatives
Todd, Matthew Zagorey ; Hrdina, Radim (advisor) ; Rýček, Lukáš (referee)
Undirected functionalization of adamantane by electrophilic oxidation proceeds mainly at the tertiary positions, owing to the higher reactivity of its C-H bonds and stability of electron deficient species, relative to the secondary positions. Ring contraction and expansion methods have been shown as a powerful tool to prepare such derivatives avoiding the reactivity constraints of undirected electrophilic oxidation reactions. Previous ring contraction methods proceeded under harsh conditions limiting their scope to simple alkyl substituents. In this work a new ring contraction method for the preparation of noradamantane derivatives from adamantane under mild conditions has been developed, enabling the presence of additional functional groups during the process. The new method utilizes the commercially available Burgess reagent for mild dehydration conditions of the starting material leading to 1,3- and 3,7-disubstituted (3-noradamantyl)methylene aldehydes, that were previously hard to obtain, if not unobtainable, and post functionalized to their corresponding protected amino-alcohols and diols. The method was also applied for the synthesis of protoadaman-4-one that is mainly synthesized through the deamination of 2-aminoadamantan-1-ol. The deamination method was also optimized for the preparation...
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