The synthesis and photochemistry of some nitrogen heterocycles

• Main Author: Hutchins, Michael
• Published: University of Bath 1983
• Subjects: 547; Organic chemistry
• Online Access: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.331641

The work described in this thesis was carried out between October, 1979 and September, 1982. Several areas of chemistry have been covered and, despite the fact that there are some common factors linking them, it has been found most convenient to classify the work under two broad headings. The first three chapters describe an investigation into the low potential anodic cyclisation of laudanosine to O-methylflavinantine. This reaction has previously been studied comprehensively by Miller who has proposed a rather unusual mechanism to account for certain features of the cyclisation. Chapter 3 of this thesis describes the generation, by non-electrochemical means, of a key intermediate in Miller's proposed mechanism. This intermediate has been shown not to cyclise in the predicted manner and so, to explain our observations, a new mechanism for the low potential transformation of laudanosine to O-methyl-flavinantine has been put forward. Chapters 4, 5 and 6 are concerned with the application of dienamide photocyclisations to the synthesis of polycyclic indole derivatives. This technique has been used successfully to prepare a number of novel polycyclic indoles, some of which we expect to show anticancer activity. The development of a new synthetic route to the anti-cancer active indolo[2,3-c] isoquinolines has also been attempted. As part of this work, it became necessary to investigate certain aspects of the chemistry of 2-aminoindoles. Our efforts towards a novel and efficient synthesis of these unstable compounds, via N-phenylsulphonyl-2-lithioindole, are therefore recorded.