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Total synthesis of macrocyclic bisbibenzyl natural products

Total synthesis of macrocyclic bisbibenzyl natural products
Total synthesis of macrocyclic bisbibenzyl natural products
This thesis is concerned with the total synthesis of two related macrocyclic natural products, cavicularin and riccardin C. Cavicularin is particularly noteworthy owing to its interesting structure: its 14-membered macrocyclic core imparts sufficient strain on the system to force one of the arenes in this paracycophane to adopt a boat-shaped conformation, deviating from planarity. The natural product also exhibits optical activity despite containing no chiral centres, this being due to axial and planar chirality in the molecule. Herein, routes to these two natural products are presented. Key steps include a highly chemoselective hydrogenation and a Wittig macrocyclisation and, in the case of cavicularin, regioselective halogenation and radical induced transannular ring contraction. This work also furnished a number of highly strained macrocycles as precursors to the natural products. These structures were found to contain boat-shaped aromatic rings, in addition to twisted olefin functionalities. A discussion of these features is presented in Chapter 6, with full crystallographic data provided in the Appendix. A review of these and related bisbibenzyl natural products is presented in Chapter 1, including their isolation, characterisation, an overview of their biological activity and previous synthetic work. Experimental procedures and characterisation data are provided in Chapter 7
Kostiuk, Sarah Louise
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Kostiuk, Sarah Louise
0da0d59a-8c15-4b22-ae26-a9ed521de8e0
Whitby, Richard J.
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Kostiuk, Sarah Louise (2009) Total synthesis of macrocyclic bisbibenzyl natural products. University of Southampton, Chemistry, Doctoral Thesis, 244pp.

Record type: Thesis (Doctoral)

Abstract

This thesis is concerned with the total synthesis of two related macrocyclic natural products, cavicularin and riccardin C. Cavicularin is particularly noteworthy owing to its interesting structure: its 14-membered macrocyclic core imparts sufficient strain on the system to force one of the arenes in this paracycophane to adopt a boat-shaped conformation, deviating from planarity. The natural product also exhibits optical activity despite containing no chiral centres, this being due to axial and planar chirality in the molecule. Herein, routes to these two natural products are presented. Key steps include a highly chemoselective hydrogenation and a Wittig macrocyclisation and, in the case of cavicularin, regioselective halogenation and radical induced transannular ring contraction. This work also furnished a number of highly strained macrocycles as precursors to the natural products. These structures were found to contain boat-shaped aromatic rings, in addition to twisted olefin functionalities. A discussion of these features is presented in Chapter 6, with full crystallographic data provided in the Appendix. A review of these and related bisbibenzyl natural products is presented in Chapter 1, including their isolation, characterisation, an overview of their biological activity and previous synthetic work. Experimental procedures and characterisation data are provided in Chapter 7

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Published date: 29 September 2009
Organisations: University of Southampton

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Local EPrints ID: 193731
URI: http://eprints.soton.ac.uk/id/eprint/193731
PURE UUID: a4b91de8-4204-49dd-8884-059b06b04397
ORCID for Richard J. Whitby: ORCID iD orcid.org/0000-0002-9891-5502

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Date deposited: 19 Jul 2011 13:37
Last modified: 30 Jan 2020 01:24

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Contributors

Author: Sarah Louise Kostiuk
Thesis advisor: Richard J. Whitby ORCID iD

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