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The ability to recognize hidden symmetry in a highly asymmetric world is a key factor in how we view and understand the world around us. Despite the fact that it is an intrinsic property of the natural world, we have an innate ability to find hidden symmetry in asymmetric objects. The inherent asymmetry of the natural world is a fundamental property built into its chemical building blocks (e.g., proteins, carbohydrates, etc.). This review highlights the role of asymmetry in the structure of the carbohydrates and how these stereochemical complexities present synthetic challenges. This survey starts with an overview of the role synthetic chemistry plays in the discovery of carbohydrates and their 3D structure. This review then introduces various de novo asymmetric synthetic approaches that have been developed for the synthesis of carbohydrates and, in particular, oligosaccharides. The two most successful strategies for oligosaccharide synthesis rely on diastereoselective palladium-catalyzed glycosylation. The first uses an Achmatowicz reaction to asymmetrically prepare pyranose building blocks along with a substrate-controlled Pd-glycosylation. The other strategy couples a ligand-controlled Pd-glycosylation with a ring-closing metathesis for oligosaccharide assembly.
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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
