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The total synthesis of cavicularin & riccardin C

The total synthesis of cavicularin & riccardin C
The total synthesis of cavicularin & riccardin C

This thesis is concerned with the total synthesis of three natural products, the biarylheptanoid acerogenin E and the bis(bibenzyl) macrocycles cavicularin and riccardin C.  The most interesting of these from a structural perspective is cavicularin, as its macrocyclic core imparts such strain on the system that it causes one of the arenes within it to adopt a boat conformation.  It was first identified as a constituent of the liverwort Cavicularia densa within the last decade, and herein we describe the first total synthesis of this demanding natural product.  Key features of our synthesis are a McMurry macrocyclisation to form an 18 membered ring, and a radical induced transannular ring contraction to generate the strained 14-membered macrocyclic core.

Our convergent approach also allowed us to complete a short synthesis of the related bis(bibenzyl) macrocycle riccardin C.  First isolated from Reboulia hemispherica, it has since been found in a number of natural sources and has been the subject of two total syntheses.  Work directed towards acerogenin E, a natural product from the Betula species, is also described.

An overview of these and related bis(bibenzyls) and biarylheptanoids macrocyclic natural products, including their isolation, biological activity and previous synthetic work, is presented in Chapter I.  Experimental procedures and charactrisatin data are provided in  Chapter III.

University of Southampton
Woodcock, Timothy
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Woodcock, Timothy
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Woodcock, Timothy (2005) The total synthesis of cavicularin & riccardin C. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

This thesis is concerned with the total synthesis of three natural products, the biarylheptanoid acerogenin E and the bis(bibenzyl) macrocycles cavicularin and riccardin C.  The most interesting of these from a structural perspective is cavicularin, as its macrocyclic core imparts such strain on the system that it causes one of the arenes within it to adopt a boat conformation.  It was first identified as a constituent of the liverwort Cavicularia densa within the last decade, and herein we describe the first total synthesis of this demanding natural product.  Key features of our synthesis are a McMurry macrocyclisation to form an 18 membered ring, and a radical induced transannular ring contraction to generate the strained 14-membered macrocyclic core.

Our convergent approach also allowed us to complete a short synthesis of the related bis(bibenzyl) macrocycle riccardin C.  First isolated from Reboulia hemispherica, it has since been found in a number of natural sources and has been the subject of two total syntheses.  Work directed towards acerogenin E, a natural product from the Betula species, is also described.

An overview of these and related bis(bibenzyls) and biarylheptanoids macrocyclic natural products, including their isolation, biological activity and previous synthetic work, is presented in Chapter I.  Experimental procedures and charactrisatin data are provided in  Chapter III.

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Published date: 2005

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Local EPrints ID: 465584
URI: http://eprints.soton.ac.uk/id/eprint/465584
PURE UUID: 6f974219-1ff2-4f09-a85d-a89f72be1c5d

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Date deposited: 05 Jul 2022 01:55
Last modified: 16 Mar 2024 20:16

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Author: Timothy Woodcock

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