Heterobimetallic complexes in organic synthesis
David T. Rutherford
2134/35604
https://repository.lboro.ac.uk/articles/thesis/Heterobimetallic_complexes_in_organic_synthesis/9396932
Heterobimetallic cobalt-molybdenum-cyclo-penta-dienyl-alkynyl-penta-carbonyl complexes have been
demonstrated to act as efficient substrates for the Pauson–Khand cycloaddition under appropriate
conditions. The inherent chirality present in the heterobimetallic core has been shown to
efficiently promote a stereoselective variant of the Pauson–Khand reaction. The unique mode of
stereoinduction in contrast to existing methodology has enabled the first stereospecific Pauson–Khand
reaction to be realised in the absence of an external source of chirality.
The scope of heterobimetallic alkyne complexes for more general asymmetric organic synthetic
transformations has been briefly addressed. The heterobimetallic core has been shown to promote
moderate to high levels of stereocontrol on addition of nucleophiles to remote centres of
complexed propargylic aldehydes.
In light of the potential use of heterobimetallic complexes in organic synthesis a new robust and
experimentally facile route for complex generation has been developed. Employing this route
heterobimetallic complexes cim be rapidly and routinely generated avoiding specialist techniques
or apparatus.
Chapter 1 provides a brief overview of the Pauson–Khand reaction and developments in this
field.
Chapter 2 highlights our work utilising hereobimetallic alkyne complexes as substrates in the
Pauson–Khand reaction, their use in more general synthetic transformations and the development
of a facile but robust route for their synthesis.
Chapter 3 provides experimental data for our studies.
2018-10-30 16:17:34
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