Studies Related to the Michael Reaction

Brown, Hugo Lambie (1968) Studies Related to the Michael Reaction. PhD thesis, University of Glasgow.

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.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Organic chemistry
• Date of Award: 1968
• Depositing User: Enlighten Team
• Unique ID: glathesis:1968-78476
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 30 Jan 2020 15:16
• Last Modified: 30 Jan 2020 15:16
• URI: https://theses.gla.ac.uk/id/eprint/78476