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Abstract Ade novoasymmetric strategy for the synthesis ofd‐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.
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De novo asymmetric Achmatowicz approach to oligosaccharide natural products
The development and application of the asymmetric synthesis of oligosaccharides from achiral starting materials is reviewed. This de novo asymmetric approach centers around the use of asymmetric catalysis for the synthesis of optically pure furan alcohols in conjunction with Achmatowicz oxidative rearrangement for the synthesis of various pyranones. In addition, the use of a diastereoselective palladium-catalyzed glycosylation and subsequent diastereoselective post-glycosylation transformation was used for the synthesis of oligosaccharides. The application of this approach to oligosaccharide synthesis is discussed.
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- Award ID(s):
- 2102649
- PAR ID:
- 10388401
- Date Published:
- Journal Name:
- Chemical Communications
- Volume:
- 58
- Issue:
- 93
- ISSN:
- 1359-7345
- Page Range / eLocation ID:
- 12913 to 12926
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D2CC05280F
