Tropylium-Catalyzed Domino Reactions for the Thioetherification of Levoglucosenone

Alexander J. Notzon; Oscar Lamb; Christopher J. Sumby; Amir Karton; Robert J. O’Reilly; Ben W. Greatrex

doi:10.1055/a-2669-5931

Synthesis, Inhaltsverzeichnis

Synthesis
DOI: 10.1055/a-2669-5931

Paper

Tropylium-Catalyzed Domino Reactions for the Thioetherification of Levoglucosenone

Alexander J. Notzon

¹Science and Technology, University of New England, Armidale, Australia

,

Oscar Lamb

²Faculty of Medicine and Health, University of New England, Armidale, Australia

,

Christopher J. Sumby

³Department of Chemistry and the Centre for Advanced Nanomaterials, School of Physics, Chemistry and Earth Sciences, University of Adelaide, Adelaide, Australia

,

Amir Karton

¹Science and Technology, University of New England, Armidale, Australia

,

Robert J. O’Reilly

¹Science and Technology, University of New England, Armidale, Australia

,

Ben W. Greatrex

²Faculty of Medicine and Health, University of New England, Armidale, Australia

› Institutsangaben

Abstract

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Abstract

Approaches to substitute the chiral platform chemicals levoglucosenone and Cyrene with aryl and alkylthiols have been developed via the α-haloketones. Substitution of the 3-chloroalkene was catalyzed by Lewis acids, with the tropylium cation showing excellent activity and yield. When thiolate was replaced with methoxide, an alkoxyoxirane could be isolated, suggesting an analogous mechanism for the thiol substitution reaction. Substitution of the 3-bromo derivative of Cyrene with thiolate nucleophiles proceeded with retention of configuration in high yield, with an intermediate oxirane also demonstrated when using methoxide. Computed LUMO energies for the α-haloketones support pathways dependent on the type of halogen, with large contributions at the carbonyl, and a sterically inaccessible σ* orbital due to the bicyclic ring system.

Keywords

Levoglucosenone - Tropylium - Oxirane - Cyrene - Thiols - Domino reaction

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