Use this URL to cite or link to this record in EThOS: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.795628
Title: Studies related to the Michael reaction
Author: Brown, Hugo Lambie
Awarding Body: University of Glasgow
Current Institution: University of Glasgow
Date of Award: 1968
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Abstract:
Part I thermal Michael reaction has been investigated from the point of view of both scope and mechanism. The reaction has been shown to be of considerable synthetic usefulness wherever the active methylene compound used is capable of facile enamine formation. The mechanism of the reaction has been shown to involve the initial attack of the Mannich base on the active methylene compound, followed by decomposition of the adduct to give a vinyl ketone and a carbinolamine. The reaction is completed by formation of an enamine from the carbin-olamine and alkylation of this by the vinyl ketone, the water produced in the dehydration of the carbinolamine serving to hydrolyse the resultant alkylated enamine. Consistent with this mechanism, the general pattern of oreintation parallels that of enamine chemistry, with allowance being made for the elavated temperatures involved in the thermal reaction. Part II Synthetic approaches to a proposed intermediate in sesquiterpene biogenesis have been only partially successful. After the facile generation of a suitably substituted seven-membered ring, difficulty has been encountered in the transformation of a 1,1-diester into a 1-keto function in a 2-substituted cycloheptene. The conformational complexities of such compounds have been investigated in the development of a viable synthetic route for this transformation. Later, problems have been encountered in the alkylation of a 2-substituted cycloheptanone to form a six-carbon side chain.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.795628  DOI: Not available
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