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The enantioselective synthesis of a[alpha],a[alpha],́b[beta],b[beta]-́tetrafluoroethylidene substituted carbohydrates

The enantioselective synthesis of a[alpha],a[alpha],́b[beta],b[beta]-́tetrafluoroethylidene substituted carbohydrates
The enantioselective synthesis of a[alpha],a[alpha],́b[beta],b[beta]-́tetrafluoroethylidene substituted carbohydrates

The syntheses of a number of tetrafluoroethylidene substituted carbohydrates are disclosed. From a commercially available fluorinated building block chirality is introduced by way of an asymmetric dihydroxylation (AD). We also disclose the beginnings of work towards the synthesis of fluorinated chiral ligands designed for use in this AD.

The chiral 1,2-diol obtained from the AD is selectively protected at either the primary or secondary alcohol to form the central intermediate our our syntheses. The functionalisation and subsequent cyclisation of these compounds are disclosed. To synthesise compounds with the tetrafluoroethylidene unit proximal to the anomeric centre we utilised a novel halogen-lithium exchange/cyclisation procedure. This reaction is shown to have wide scope being used to synthesise hexoses and pentoses in both their pyranose and hexose forms.

The intermediate is also shown to take part in a radical addition/atom transfer/nucleophilic cyclisation sequence to form tetrafluoroethylidene substituted carbohydrates where the fluorinated substituent is remote from the anomeric centre.

We also disclose the synthesis of a tetrafluoroethylidene substituted nucleoside and glycal.

University of Southampton
Boydell, A. James
e7ecce9e-6700-4ace-91e6-cc648b353caf
Boydell, A. James
e7ecce9e-6700-4ace-91e6-cc648b353caf

Boydell, A. James (2007) The enantioselective synthesis of a[alpha],a[alpha],́b[beta],b[beta]-́tetrafluoroethylidene substituted carbohydrates. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

The syntheses of a number of tetrafluoroethylidene substituted carbohydrates are disclosed. From a commercially available fluorinated building block chirality is introduced by way of an asymmetric dihydroxylation (AD). We also disclose the beginnings of work towards the synthesis of fluorinated chiral ligands designed for use in this AD.

The chiral 1,2-diol obtained from the AD is selectively protected at either the primary or secondary alcohol to form the central intermediate our our syntheses. The functionalisation and subsequent cyclisation of these compounds are disclosed. To synthesise compounds with the tetrafluoroethylidene unit proximal to the anomeric centre we utilised a novel halogen-lithium exchange/cyclisation procedure. This reaction is shown to have wide scope being used to synthesise hexoses and pentoses in both their pyranose and hexose forms.

The intermediate is also shown to take part in a radical addition/atom transfer/nucleophilic cyclisation sequence to form tetrafluoroethylidene substituted carbohydrates where the fluorinated substituent is remote from the anomeric centre.

We also disclose the synthesis of a tetrafluoroethylidene substituted nucleoside and glycal.

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Published date: 2007

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Local EPrints ID: 466302
URI: http://eprints.soton.ac.uk/id/eprint/466302
PURE UUID: 9ae8a0b5-3fe1-4432-b6d6-b1ec0c9c28b3

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Date deposited: 05 Jul 2022 05:07
Last modified: 16 Mar 2024 20:37

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Author: A. James Boydell

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