New reactions of metal-alkyne complexes
thesisposted on 06.08.2013 by Ryan J. Davoile
In order to distinguish essays and pre-prints from academic theses, we have a separate category. These are often much longer text based documents than a paper.
This thesis describes the use of bimetallic alkyne complexes for use in variants of the Nicholas reaction. The heterobimetallic core provides a source of chiral control unlike previous protocols reported in the literature, as stereocontrol arises from the inherently chiral cobalt-molybdenum core of these complexes and not from an external source. The inherently chiral heterobimetallic complexes were utilised as efficient chiral auxiliaries for nucleophilic additions to both propargylic alkene and Nicholas salt complexes with a degree of stereocontrol also extending to intramolecular addition. 1,3-Dipolar cycioaddition to homo bimetallic and heterobimetallic enyne complexes to obtain isoxazoline ring systems was investigated, following a report in the literature. A novel homobimetallic 1,3-dipole was synthesised on opening of a cyclopropane, subsequel1tly trapping with a series of aldehyde and imines to efficiently form tetrahydrofuran and pyrrolidine ring structures. Chapter 1: An overview of developments of homobimetallic alkyne complexes in the Nicholas reaction as reported in the literature. Chapter 2: Highlights our research into the use of bimetallic alkyne complexes for use in organic synthesis. Chapter 3: Provides experimental data for our studies.