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Title: New gas-phase cascade reactions of stabilising phosphorus ylides leading to ring-fused indoles and quinolines
Author: Murray, Lorna
ISNI:       0000 0004 2719 8491
Awarding Body: University of St Andrews
Current Institution: University of St Andrews
Date of Award: 2010
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Synthesis and flash vacuum pyrolysis (FVP) of stabilised phosphorus ylides containing an o-amino functionalised benzene ring has been examined for the first time. Model studies using N-methyl-N-tosyl and N-mesyl-N-methyl ylides showed that the ylides could be prepared, although yields were variable, and had the expected spectroscopic properties. Upon FVP, however, the expected loss of Ph₃PO and the sulfonyl group was accompanied by unexpected transfer of the reactive site from nitrogen to carbon giving 3- substituted quinolines rather than the expected indole products. Moving to ylides with an α-cinnamoyl group (or heterocyclic analogue) did, however, result in the originally planned tandem cyclisation leading to ring-fused carbazole products. N-Benzyl was also found to be a suitable thermally labile group and a series of α-cinnamoyl N-benzyl-N-methyl ylides were prepared and characterised. For their synthesis, use of N-cinnamoylbenzotriazoles was found to be preferable to cinnamoyl chloride, requiring only half the amount of amino-functionalised phosphonium salt. While FVP of some of these ylides led to benzo-, furo- and thienocarbazoles in good yield, others again gave quinoline-type products pointing to a fine balance between the two alternative modes of cyclisation. It was noted that one of the furocarbazole products was very similar to a natural product, Eustifoline D, isolated from the medicinally active shrub Murraya euchrestifolia from Taiwan and its synthesis was planned. With a view to producing the required N-H carbazole, N,N-dibenzylamino amino ylides were prepared and were found to exhibit restricted rotation leading to broad NMR signals. Their FVP again led to both quinoline and carbazole products, with the former having usually, but not always, lost a phenyl group. Mechanistic pathways for the formation of the various products are proposed. Complete assignment of the complex ¹H NMR spectra of the various fused-ring heterocyclic products was achieved, assisted by simulations in many cases. The ylide precursor required for Eustifoline D was prepared in five steps and 10% overall yield from 5-methylanthranilic acid. The final FVP step gave a quinoline as the major product, but the minor product was Eustifoline D, spectroscopically identical to the natural product.
Supervisor: Aitken, R. Alan Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD305.P46M8 ; Organophosphorus compounds ; Ylides ; Pyrolysis ; Indole ; Quinoline