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Novel cascade aryne-capture/rearrangement reactions

Pocock, Ian (2014) Novel cascade aryne-capture/rearrangement reactions. Doctoral thesis, University of Huddersfield.

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Arynes are reactive intermediates that have been an academic curiosity for over a century. A recent renaissance of interest in the chemistry of these intermediates can be traced back to the development of ortho-(silyl)aryl triflates as aryne precursors. The application of aryne chemistry outside academia has been precluded by the expense and laborious preparation of these precursors.
Diphenyliodonium-2-carboxylate has been shown to be a stable and inexpensive benzyne precursor, however application has been limited due to the high temperature (>160 ºC) and long reaction times required to generate benzyne by this protocol. Described within is an investigation whereby diphenyliodonium-2-carboxylate is successfully decomposed using microwave irradiation to generate benzyne. This proof of concept investigation shows diphenyliodonium-2-carboxylate can be applied as an off-the-shelf benzyne precursor; by using microwave radiation, significantly reduced reaction times and lower b.p. solvents can facilitate a more universal application of this protocol than previously described.
The investigation into the reactions of allylamino malonates with arynes is also described. Simple allylamino malonates are shown to perform a novel cascade aryne capture/ring-closure/[2,3]-rearrangement to generate indolin-3-one products. The influence of substitution of the indolin-3-one products on the photophysical properties is probed. Tetrahydropyridine derived aminomalonates result in a ring contraction by [2,3]-rearrangement to N-phenyl pyrrolidine products.
Further investigations show N-allyl proline methyl esters also generate indolin-3-one products by this novel cascade mechanism. The photophysical properties of these products are also probed. N-diallylalanine methyl ester is shown to generate indolin-3-one with benzyne however N-allyl sarcosine ethyl ester generates the N-phenyl -allylated amino esters product by aryne capture/[2,3]-rearrangement.

Item Type: Thesis (Doctoral)
Subjects: Q Science > QD Chemistry
Depositing User: Elizabeth Boulton
Date Deposited: 10 Mar 2015 16:11
Last Modified: 06 Nov 2015 01:42


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