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New syntheses of the macrocyclic bisbibenzyl natural products, riccardin D, riccardin C, polymorphatin A and an unnatural analogue; formal total syntheses of cavicularin and asterelin A

New syntheses of the macrocyclic bisbibenzyl natural products, riccardin D, riccardin C, polymorphatin A and an unnatural analogue; formal total syntheses of cavicularin and asterelin A
New syntheses of the macrocyclic bisbibenzyl natural products, riccardin D, riccardin C, polymorphatin A and an unnatural analogue; formal total syntheses of cavicularin and asterelin A
This thesis describes total syntheses of many different macrocyclic bisbibenzyl natural products including riccardin D 1.1, riccardin C 1.2, asterelin A 1.4, cavicularin 1.5 and polymorphatin A 1.6 as well as an unnatural macrocyclic bisbibenzyl analogue 1.3.

The first approach developed a strategy for the total synthesis of riccardin D 1.1. The key fragments in the target are synthesised then connected using a Heck reaction. An intramolecular Wittig reaction is then used to achieve macrocyclisation.

The second approach provides access to many natural products in the macrocyclic bisbibenzyl family, including riccardin C 1.2, asterelin A 1.4 and cavicularin 1.5 as well as an unnatural analogue 1.3. We have synthesised and connected the key fragments of each target. To close the macrocyclic ring, we have demonstrated for the first time a new strategy involving an alkyllithium mediated displacement reaction to make the macrocycle via a Corey Seebach reaction. We have used the method to complete total syntheses of riccardin C 1.2 and an unnatural analogue 1.3. The work additionally constitutes formal total syntheses of asterelin A 1.4 and cavicularin 1.5.

The third approach provided a method to achieve the first total synthesis of polymorphatin A 1.6. A nickel-mediated cross-coupling reaction was used to effect macrocyclisation and install the strained biaryl linkage connecting its two distorted arenes.
University of Southampton
Almalki, Faisal Ateeq A.
099cf883-b9f3-4a16-a4b2-38b272ed3ec4
Almalki, Faisal Ateeq A.
099cf883-b9f3-4a16-a4b2-38b272ed3ec4
Harrowven, David
bddcfab6-dbde-49df-aec2-42abbcf5d10b

Almalki, Faisal Ateeq A. (2017) New syntheses of the macrocyclic bisbibenzyl natural products, riccardin D, riccardin C, polymorphatin A and an unnatural analogue; formal total syntheses of cavicularin and asterelin A. University of Southampton, Doctoral Thesis, 259pp.

Record type: Thesis (Doctoral)

Abstract

This thesis describes total syntheses of many different macrocyclic bisbibenzyl natural products including riccardin D 1.1, riccardin C 1.2, asterelin A 1.4, cavicularin 1.5 and polymorphatin A 1.6 as well as an unnatural macrocyclic bisbibenzyl analogue 1.3.

The first approach developed a strategy for the total synthesis of riccardin D 1.1. The key fragments in the target are synthesised then connected using a Heck reaction. An intramolecular Wittig reaction is then used to achieve macrocyclisation.

The second approach provides access to many natural products in the macrocyclic bisbibenzyl family, including riccardin C 1.2, asterelin A 1.4 and cavicularin 1.5 as well as an unnatural analogue 1.3. We have synthesised and connected the key fragments of each target. To close the macrocyclic ring, we have demonstrated for the first time a new strategy involving an alkyllithium mediated displacement reaction to make the macrocycle via a Corey Seebach reaction. We have used the method to complete total syntheses of riccardin C 1.2 and an unnatural analogue 1.3. The work additionally constitutes formal total syntheses of asterelin A 1.4 and cavicularin 1.5.

The third approach provided a method to achieve the first total synthesis of polymorphatin A 1.6. A nickel-mediated cross-coupling reaction was used to effect macrocyclisation and install the strained biaryl linkage connecting its two distorted arenes.

Text
FAA_Thesis_with_the_amendments - Version of Record
Restricted to Repository staff only until 15 September 2020.
Available under License University of Southampton Thesis Licence.

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Published date: September 2017

Identifiers

Local EPrints ID: 418156
URI: https://eprints.soton.ac.uk/id/eprint/418156
PURE UUID: 68df54c5-c471-4758-a040-56cc56c4a55e
ORCID for David Harrowven: ORCID iD orcid.org/0000-0001-6730-3573

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Date deposited: 22 Feb 2018 17:32
Last modified: 14 Mar 2019 01:52

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