The University of Southampton
University of Southampton Institutional Repository

Organozirconium approaches to small molecule synthesis

Henderson, Alan Robert (2012) Organozirconium approaches to small molecule synthesis University of Southampton, School of Chemistry, Doctoral Thesis , 207pp.

Record type: Thesis (Doctoral)


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 ?2-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 ?-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.

PDF Alan_Henderson_Thesis.pdf - Other
Download (4MB)

More information

Published date: 31 January 2012
Organisations: University of Southampton, Chemistry


Local EPrints ID: 334908
PURE UUID: d52e9713-e5bf-4ee8-8c2d-234d7401f1e1
ORCID for Richard Whitby: ORCID iD

Catalogue record

Date deposited: 29 Mar 2012 15:36
Last modified: 18 Jul 2017 06:11

Export record


Author: Alan Robert Henderson
Thesis advisor: Richard Whitby ORCID iD

University divisions

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton:

ePrints Soton supports OAI 2.0 with a base URL of

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.