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Title: Some synthetic applications of the chemistry of 3-oxidopyridiniums and pyrido-oxepino [3,2-b] indoles.
Author: Ashcroft, William Robert
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 1981
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Chapter 1 The first section outlines the general approach developed in these laboratories over the past years to the preparation of synthetically useful 6-membered cyclic enamines from their readily available allylamine isomers for use in alkaloid synthesis. The second section provides an estimation of the relative stabilities of some enamine/ allylamine pairs of interest in later chapters by means of molecular orbital calculations. Chapter 2 describes attempts to prepare a synthetically useful 5-membered cyclic enamine from its allylamine isomer in an extension of the Chemistry discussed in Chapter 1. Chapter 3 describes an approach to the synthesis of a model tetracyclic compound with the eventual aim of a total synthesis of one of the alkaloids of the akuammiline group utilising the methodology described in Chapter 1 and modifications suggested from the findings with further model compounds in Chapter 4. Chapter 4 bears a description of a total synthesis of the indole alkaloid deplancheine utilising a previously unknown tetracyclic ketone which was itself prepared simply and efficiently from a protected 3-oxidopyridinium salt by means of a modified form of the general approach discussed in Chapters 1 and 3. Also included is a discussion of an approach to the synthesis of another indole alkaloid, antirhine, from the same tetracyclic ketone. Chapter 5 describes an investigation into the generality and mechanism of formation of some unexpected products derived from complex metal hydride reduction of various 1-substituted-3-oxidopyridiniums. Chapter 6 describes a re-examination of the rearrangement reactions of pyrido-oxepino-indoles previously reported in these laboratories and does indeed confinn the products to be the valuable synthetic intennediate ellipticine quinone and analogues, and further that the rearrangements are entirely regiospecific. Also described are some new short regioselecti ve methods of preparation of the pyridine of phthalide required in the pyrido-oxepino-indole syntheses.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available