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Lookup NU author(s): Dr Jay Tromans, Bian Zhang, Emeritus Professor Bernard Golding
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.Vinyl ethers are valuable synthetic intermediates which are also found as natural products, including aflatoxins, rifamycins and plasmalogens. The latter are ubiquitous phospholipids in human cells and contain a vinyl ether moiety with specifically Z configuration. Although numerous methods are available for synthesis of vinyl ethers, there is a lack of methods for obtaining Z isomers of molecules of the type RCH=CHOR’ that are applicable to plasmalogens. A variant of the Peterson reaction is described that generates such molecules with very high stereoselectivity (Z/E ratio: 99 : 1). (R,R)/(S,S)-1-alkoxy-2-hydroxyalkylsilanes were synthesized from 1-trimethylsilylalkynes by a sequence of reduction with di-isobutylaluminium hydride to a (Z)-1-trimethylsilylalkene, epoxidation of the alkene to a 2-trimethylsilyl-3-substituted epoxide and regioselective, boron-trifluoride catalyzed ring-opening of the epoxide by reaction with an alcohol. Conversion of the (R,R)/(S,S)-1-alkoxy-2-hydroxyalkylsilanes to vinyl ethers (RCH=CHOR’) was achieved under basic conditions as in a standard Peterson reaction. However, near exclusive formation of a Z vinyl ether was only achieved when the reaction was performed using potassium hydride in the non-polar solvent α,α,α-trifluorotoluene, more polar solvents giving increasing amounts of the E isomer. The sequence described embraces a variety of substituents and precursors, proceeds in overall high yield and is readily scalable.
Author(s): Tromans J, Zhang B, Golding BT
Publication type: Article
Publication status: Published
Journal: Chemistry - A European Journal
Year: 2024
Volume: 30
Issue: 2
Print publication date: 08/01/2024
Online publication date: 21/09/2023
Acceptance date: 21/09/2023
Date deposited: 22/11/2023
ISSN (print): 0947-6539
ISSN (electronic): 1521-3765
Publisher: John Wiley and Sons Inc
URL: https://doi.org/10.1002/chem.202302708
DOI: 10.1002/chem.202302708
Data Access Statement: The data that support the findings of this study are available from the corresponding author upon reasonable request
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