Date of Award

9-13-2019

Publication Type

Doctoral Thesis

Degree Name

Ph.D.

Department

Chemistry and Biochemistry

First Advisor

Green, J.

Rights

info:eu-repo/semantics/openAccess

Creative Commons License

Creative Commons Attribution-Noncommercial-No Derivative Works 4.0 License
This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 4.0 License.

Abstract

The Nazarov cyclization reaction has been used as an effective method to synthesize cyclopentanones. While 6-membered ring systems can be available by way of the homo Nazarov variant, 7-membered ring formation involving a Nazarov-type reaction is very rare, and completely unknown thermally. Using the established concept of the ability of the alkyne-Co2(CO)6 moiety to enable the formation of -carbonyl cations and the good stability of this generated cation, 7-membered ring formation via the vinylogous Nazarov reaction with electron deficient enones has been investigated. The desired aryl substituted enyone-Co2(CO)6 complex precursors for the cyclization reaction have been prepared from commercially available starting materials, using a series of reactions that include Sonogashira cross-coupling, desilylation, organolithium reactions with aldehydes, oxidation and complexation reactions. The treatment of the respective complex precursors, using SnCl4 as a suitable Lewis acid, successfully generated cycloheptynone-Co2(CO)6 complexes. The substitution effects have been examined, showing that introducing a bulky group at the alpha-position to the carbonyl enhances the cyclization efficiency by enabling the desired s-trans/s-trans conformation. On the other hand, beta-substituting with an R group other than H atom reduces the reaction rate and allows formation of the desired 7-membered ring only in very low yield. Preparation of appropriate dienynone-Co2(CO)6 complex substrates allowed expansion of the reaction scope to non-aromatic starting materials. Successful reductive decomplexation of the cycloheptynone-Co2(CO)6 unit also was demonstrated.

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