Novel radical and palladium cyclisation reactions

Penfold, David John (1998) Novel radical and palladium cyclisation reactions. University of Southampton, Doctoral Thesis.

Abstract

This thesis is concerned with the synthesis of a range of substrates suitable for specific radical and palladium mediated cyclisation reactions and the investigation of the behaviour of these substrates in those cyclisation reactions.

Chapter two details work carried out in order to develop a cascade radical reaction as a route to polycyclic structures. Central to this scheme was the use of intramolecular vinyl radical attack at a cyclic ketone, followed by ring expansion. Specific attention was given to a range of substrates used in model studies in order to gain a fuller understanding of intramolecular vinyl radical attack onto a cyclic ketone and subsequent ring expansion.

Chapter three is concerned with the use of radical initiated cascade reactions to generate tricyclic β-lactam structures. Central to this work was the implementation of intramolecular radical attack at a methylenecyclopropane unit and subsequent ring expansion. Two general schemes were investigated, each providing novel tricyclic β-lactams.

Chapter four gives a general introduction to the use of palladium and nickel catalysed cycloaddition reactions of methylenecyclopropanes. Particular attention is given to intramolecular cyclisations.

Chapter five covers work carried out to investigate palladium catalysed intramolecular [3+2] cycloaddition reactions of methylenecyclopropane b-lactams as a route to tricyclic β-lactam structures. A range of substrates were synthesised, but none of these gave the desired intramolecular cyclisation. Despite this, two unprecedented palladium catalysed reactions of methylenecyclopropanes were observed.

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