An organocatalytic asymmetric approach to chiral proline derived diketopiperazines related to the prenylated indole alkaloid family

Rees, Matthew (2018). An organocatalytic asymmetric approach to chiral proline derived diketopiperazines related to the prenylated indole alkaloid family. University of Birmingham. Ph.D.

[img]
Preview
Rees18PhD.pdf
PDF - Accepted Version

Download (8MB)

Abstract

The prenylated indole alkaloids are a large family of natural products that have been isolated from various marine and terrestrial strains of Penicillium, Aspergillus and Malbranchea fungi. These compounds possess complex polycyclic structures including a characteristic bicyclo[2.2.2]diazaoctane core and have displayed wide-ranging biological activities. Chapter 1 gives an introduction to the prenylated indole alkaloids and important synthetic strategies to the key bicyclic core and an overview of previous work from our research group in this area.

Recent work showed that triketopiperazines will undergo highly enantioselective Michael-additions and Michael addition–ring-closure reactions, efficiently generating compounds possessing the bicyclo[2.2.2]diazaoctane core found in the natural products. Chapter 2 discusses the extension of previous methodology towards a bicyclic triketopiperazine derived from proline including its synthesis and successful implementation in asymmetric Michael additions.

Chapter 3 then explores the Michael addition–ring-closure of the proline derived triketopiperazine which was found to give highly enantioselective and high yielding access to hydroxy diketopiperazines possessing the key bicyclo[2.2.2]diazaoctane. The chapter also contains further transformations towards the natural product scaffold including a radical Barton-McCombie deoxygenation.

Chapter 4 focusses on a novel Michael–Michael cascade strategy for the synthesis of molecules possessing the bicyclo[2.2.2]diazaoctane core of the prenylated indole alkaloids.

Type of Work: Thesis (Doctorates > Ph.D.)
Award Type: Doctorates > Ph.D.
Supervisor(s):
Supervisor(s)EmailORCID
Simpkins, N. S.UNSPECIFIEDUNSPECIFIED
Grainger, Richard S.UNSPECIFIEDUNSPECIFIED
Licence:
College/Faculty: Colleges (2008 onwards) > College of Engineering & Physical Sciences
School or Department: School of Chemistry
Funders: Engineering and Physical Sciences Research Council
Subjects: Q Science > QD Chemistry
URI: http://etheses.bham.ac.uk/id/eprint/8628

Actions

Request a Correction Request a Correction
View Item View Item

Downloads

Downloads per month over past year