Chiral Materials from Biomass: 3-deoxy-α-D-ribono-1,4-lactone and 3-deoxy-α-D-arabino-1,4-lactone via the Bromination of Cyrene

Date

2025

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Puschnig, J.
Sumby, C.J.
Greatrex, B.W.

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European Journal of Organic Chemistry, 2025; 28(19):e202500010-1-e202500010-5

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Johannes Puschnig, Christopher J. Sumby, Ben W. Greatrex

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Abstract

The feeding modulator 3-deoxy-d-arabino-1,4-lactone and the diastereomer 3-deoxy-d-ribono-1,4-lactone have been prepared from the biomass pyrolysis product Cyrene (dihydrolevoglucoseone). The arabino-configured lactone was accessed via the diastereoselective bromination of Cyrene, through an enamine-bromination/hydrolysis strategy, giving the thermodynamically stable equatorial bromide after a base catalyzed equilibration. A Baeyer-Villiger oxidation and then reaction with benzoate followed by hydrolysis gave the target lactone. 3-Deoxy-d-ribono-1,4-lactone was accessible via the reaction of the bromide with benzoate prior to Baeyer-Villiger reaction resulting in the retention of configuration. The diastereoselectivity for the reactions and the formation of byproducts was rationalized by the involvement of an intermediate oxirane and subsequent House-Meinwald rearrangements.

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© 2025 The Author(s). European Journal of Organic Chemistry published by Wiley-VCH GmbH This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

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