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Gold catalysed intermolecular atom transfer reactions on heteroatom-substituted alkynes

Cremonesi, Alex (2013)
Ph.D. thesis, University of Birmingham.

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Abstract

In this thesis the development of several novel gold-catalysed transformations are reported. Two intermolecular atom transfer processes have been designed and developed to access gold carbenoid reactivity. The latter reactive species allowed the synthesis of various α,ß-unsaturated carboxylic acid derivatives and trisubstituted oxazoles.
Numerous nitrogen- and oxygen substituted alkynes have been prepared and employed in oxygen transfer processes promoted by gold complexes. Using pyridine \(N\)-oxide, both ynamides and ynol ethers underwent regioselective intermolecular oxidation reactions under mild gold catalysis conditions. During the transformation, an α-oxo gold carbenoid intermediate is accessed which develops through a rapid 1,2-insertion reaction to yield α,ß -unsaturated imides and vinylogous carbimates.
The strategy has proved to be a valid alternative to the use of hazardous α-oxo diazo compound when carbene reactivity is desired. Appling a similar strategy, \(N\)-imido pyridonium ylides have been used as an \(O,N\)-dipole onto gold activated ynamides and ynol ethers. The overall [3+2] cyclisation occurred through a nitrene transfer process followed by a cycloisomerisation step. Under this approach, ynamides and ynol ethers have been converted into highly functionalised trisubstituted oxazoles. The mild gold catalysis conditions allowed the use of a wide range of functionality. Moreover, the α-imido gold carbenoid involved as a reaction intermediate displayed the possibility to utilise such protocol to access α-imido carbene reactivity

Type of Work:Ph.D. thesis.
Supervisor(s):Davies, Paul
School/Faculty:Colleges (2008 onwards) > College of Engineering & Physical Sciences
Department:School of Chemistry
Subjects:QD Chemistry
Institution:University of Birmingham
ID Code:4083
This unpublished thesis/dissertation is copyright of the author and/or third parties. The intellectual property rights of the author or third parties in respect of this work are as defined by The Copyright Designs and Patents Act 1988 or as modified by any successor legislation. Any use made of information contained in this thesis/dissertation must be in accordance with that legislation and must be properly acknowledged. Further distribution or reproduction in any format is prohibited without the permission of the copyright holder.
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