New one-pot multi-reaction processes for the synthesis of highly functionalised carbocycles and heterocycles

Grafton, Mark W. (2014) New one-pot multi-reaction processes for the synthesis of highly functionalised carbocycles and heterocycles. PhD thesis, University of Glasgow.

Abstract

With the use of a one-pot process, a diastereoselective synthesis of bicyclononanes and decanes has been developed. Initial treatment of an allylic alcohol with trichloroacetonitrile, in the presence of DBU, afforded the corresponding allylic trichloroacetimidate. The trichloroacetimidate was then subjected to a one-pot process
involving a thermal Overman rearrangement, ring-closing-enyne-metathesis and a hydrogen-bond directed Diels-Alder reaction to form polycyclic products in good isolated
yields and as single diastereomers.Research was then carried out on how this process could be extended. Through the use of Grubbs second generation catalyst, the process was extended to include a cross-metathesis reaction forming highly functionalised 1,3-dienes. These 1,3-dienes were then used in the hydrogen bond directing Diels-Alder reaction to generate highly functionalised polycycles,
again as single diastereomers. This process was then employed towards the first total synthesis of the natural product, netamine A. Further studies showed that carbo- and heterocyclic 1,3-dienes could be used in a one-pot Diels-Alder reaction and aromatisation step for the rapid preparation of partially saturated indane and tetralin motifs, which are present in biologically active molecules.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: One-Pot reactions, Overman rearrangement, Enyne metathesis, Diels-Alder reaction, tandem catalysis, natural product synthesis
• Subjects: Q Science > QD Chemistry
• Colleges/Schools: College of Science and Engineering > School of Chemistry
• Supervisor's Name: Sutherland, Dr. Andrew
• Date of Award: 2014
• Depositing User: Dr Mark W. Grafton
• Unique ID: glathesis:2014-5864
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 22 Dec 2014 10:09
• Last Modified: 22 Dec 2014 10:38
• URI: https://theses.gla.ac.uk/id/eprint/5864