Synthetic and Biosynthetic Studies on Nitrogen Heterocycles

MacKinnon, John W. M (1976) Synthetic and Biosynthetic Studies on Nitrogen Heterocycles. PhD thesis, University of Glasgow.

Abstract

The reaction of nitrosocarbonyl-compounds with a series of simple dienes to form Diels-Alder adducts has been investigated. The modification of such adducts in further synthesis has been studied and their limitations assessed. A series of adducts, designed for de-acylation under a variety of mild conditions, have been formed from the novel alkyl nitrosoformate reactive intermediates and C-nitroso-formamide adducts have also been briefly examined. The chemistry of adduct formation between ergosteryl acetate and various nitrosocarbonyl-compounds has been examined in detail and a novel rearrangement discovered in this field. The synthesis of a postulated biphenyl intermediate in the biosynthesis of the Amaryllidaceae alkaloids norpluviine and lycorine has been investigated by several different routes. Tracer experiments with 3H- and 14C-tyrosine have confirmed that D- and L-tyrosine are incorporated with equal efficiency into these alkaloids and that D-tyrosine is converted into L-tyrosine before incorporation. The later stages in the biosynthesis of norpluviine and lycorine have been re-examined. A partial retention at position 2 in lycorine of tritium from [3,5-3H2]tyrosine is noted in Clivia miniata Regel and 'Twink' daffodils. Degradation studies suggest that this partial retention results from scrambling of the 2-methylene protons of norpluviine and a mechanism for this is postulated.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Organic chemistry
• Date of Award: 1976
• Depositing User: Enlighten Team
• Unique ID: glathesis:1976-78731
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 30 Jan 2020 14:58
• Last Modified: 30 Jan 2020 14:58
• URI: https://theses.gla.ac.uk/id/eprint/78731