Exploring a De Novo Route to Bradyrhizose: Synthesis and Isomeric Equilibrium of Bradyrhizose Diastereomers

A de novo asymmetric strategy for the synthesis of d‐bradyrhizose diastereomers from an achiral ketoenolester precursor is described. Key transformations used in the stereodivergent approach include two Noyori asymmetric reductions, an Achmatowicz rearrangement, diastereoselective alkene oxidations,...

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Bibliographic Details
Published in:Chemistry : a European journal 2024-06, Vol.30 (33), p.e202400886-n/a
Main Authors: Cunha, Vitor L. S., O'Doherty, George A., Lowary, Todd L.
Format: Article
Language:English
Subjects:
asymmetric synthesis
Asymmetry
bradyrhizose
carbohydrates
de novo synthesis
Diastereoisomers
Glycosylation
Natural products
Palladium
Stereoselectivity
Synthesis
total synthesis
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Summary:A de novo asymmetric strategy for the synthesis of d‐bradyrhizose diastereomers from an achiral ketoenolester precursor is described. Key transformations used in the stereodivergent approach include two Noyori asymmetric reductions, an Achmatowicz rearrangement, diastereoselective alkene oxidations, and the first example of a palladium(0)‐catalyzed glycosylation of a vinylogous pyranone. The isomeric composition of the bicyclic reducing sugars obtained was analyzed and their behaviour was compared to the natural product, revealing key stereocentres that impact the overall distribution. A de novo approach to synthesize d‐bradyrhizose diastereomers from an achiral ketoenolester is presented. The strategy uses transfer hydrogenation, an Achmatowicz rearrangement and alkene oxidations as key steps in the synthesis. The effect of the configuration at C‐2, C‐4 and C‐9 on the isomeric composition of the reducing sugars in water was analyzed and compared with the natural product.
ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.202400886