Asymmetric oxidative cyclisation of dienes
Asymmetric oxidative cyclisation of dienes
The total synthesis of the mono- THF acetogenin cis-solamin has been accomplished via an asymmetric permanganate promoted oxidative cyclisation of a 1,5-diene. The asymmetric oxidative cyclisation formed the 2,5-disubstituted THF-diol core, creating the four new stereocentres with control of absolute stereochemistry, in excellent yield (75%). For the purpose of both unequivocally determining the absolute configuration of cis-solamin and obtaining biological data, three cis-solamin diastereoisomers were selectively synthesised via our concise oxidative cyclisation methodology.
The permanganate promoted chiral phase-transfer catalysed (CPTC) oxidative cyclisation of 1,5-dienes using a cinchonidine derived tertiary ammonium salt has been investigated, realising some excellent ee’s (up to 94%). This excellent level of asymmetric induction was utilised in the formal synthesis of cis-solamin. The key steps were the CPTC oxidative cyclisation (52%, 93% ee) and the oxidative degradation of te naphthyl group to the carboxylic acid without epimerisation.
Aromatic ester and amides have shown themselves applicable to the CPTC oxidative cyclisation of 1,5-dienes, giving moderate to good asymmetric induction (up to 70% ee).
The racemic, asymmetric and CPTC permanganate promoted oxidative cyclisation of 1,6-dienes to furnish exclusively cis-THP-diols has been developed. Thus, the creation of up to four new stereocentres with complete control of relative and absolute stereochemistry has been accomplished.
University of Southampton
Cecil, Alexander Richard Liam
0b72e2b5-c24c-4d87-bc16-67c9eca7fe95
2004
Cecil, Alexander Richard Liam
0b72e2b5-c24c-4d87-bc16-67c9eca7fe95
Cecil, Alexander Richard Liam
(2004)
Asymmetric oxidative cyclisation of dienes.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The total synthesis of the mono- THF acetogenin cis-solamin has been accomplished via an asymmetric permanganate promoted oxidative cyclisation of a 1,5-diene. The asymmetric oxidative cyclisation formed the 2,5-disubstituted THF-diol core, creating the four new stereocentres with control of absolute stereochemistry, in excellent yield (75%). For the purpose of both unequivocally determining the absolute configuration of cis-solamin and obtaining biological data, three cis-solamin diastereoisomers were selectively synthesised via our concise oxidative cyclisation methodology.
The permanganate promoted chiral phase-transfer catalysed (CPTC) oxidative cyclisation of 1,5-dienes using a cinchonidine derived tertiary ammonium salt has been investigated, realising some excellent ee’s (up to 94%). This excellent level of asymmetric induction was utilised in the formal synthesis of cis-solamin. The key steps were the CPTC oxidative cyclisation (52%, 93% ee) and the oxidative degradation of te naphthyl group to the carboxylic acid without epimerisation.
Aromatic ester and amides have shown themselves applicable to the CPTC oxidative cyclisation of 1,5-dienes, giving moderate to good asymmetric induction (up to 70% ee).
The racemic, asymmetric and CPTC permanganate promoted oxidative cyclisation of 1,6-dienes to furnish exclusively cis-THP-diols has been developed. Thus, the creation of up to four new stereocentres with complete control of relative and absolute stereochemistry has been accomplished.
Text
932701.pdf
- Version of Record
More information
Published date: 2004
Identifiers
Local EPrints ID: 465248
URI: http://eprints.soton.ac.uk/id/eprint/465248
PURE UUID: 768fee1e-ccd4-4637-b945-cf8a6a64a51c
Catalogue record
Date deposited: 05 Jul 2022 00:31
Last modified: 16 Mar 2024 20:03
Export record
Contributors
Author:
Alexander Richard Liam Cecil
Download statistics
Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.
View more statistics