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Title: Organozirconium approaches to small molecule synthesis
Author: Henderson, Alan Robert
ISNI:       0000 0004 2715 8801
Awarding Body: University of Southampton
Current Institution: University of Southampton
Date of Award: 2012
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A review of zirconocene mediated intramolecular cocyclisations and the elaboration of the resultant zirconacycles is presented as a background to the work presented in this thesis. The first area of novel work is the attempted intramolecular trapping of zirconocene η2-alkene complexes, generated by an unprecedented endocyclic cyclometallation, with a pendant alkyne. A series of inter- and intramolecular transformations other than the desired transformation were observed. The second area of work presented is the synthesis and biological testing of two ligands for receptors from the NR4A subfamily of orphan nuclear receptors. Our interest in this area stemmed from previous work in our group on the zirconocene mediated synthesis of ligands for receptors in the NR5 subfamily. The third area of research presented is the zirconocene mediated cocyclisation of a series of novel ynamides and elaboration of the resulting zirconacyclopentadienes. Also presented in this chapter is the use of the exocyclic dienes formed through protonolysis of the zirconacyclopentadienes in a series of Diels-Alder reactions in excellent regio- and stereoselectivity. The penultimate area of research is the first total synthesis of (+)-mucosin utilising a zirconocene mediated cocyclisation of a diene followed by the insertion of an α-silyl alkyl carbenoid to gain the major diastereoisomer with the correct stereochemistry of the four contiguous stereocentres. The route taken to (+)-mucosin can be easily adapted in order for the synthesis of the natural product (−)-mucosin to be realised. Finally the well established chemistries of carbenoid insertion and isonitrile insertion into zirconacyclopentanes are combined in order to furnish a series of novel cyclohexanones.
Supervisor: Whitby, Richard Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry