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DOI: 10.1055/a-2791-8016
Silicon as a Strategic Element in Carbohydrate Chemistry: Glycomimetic Design, Reductive Migration, and Ring Editing
Authors
This work was supported by the National Science Foundation (CHE- 2246828). This work utilized the Alpine high performance computing resource at the University of Colorado Boulder. Alpine is jointly funded by the University of Colorado Boulder, the University of Colorado Anschutz, and Colorado State University and with support from NSF grants OAC-2201538 and OAC-2322260.
Abstract
Silicon offers a powerful yet underexplored handle for re-engineering carbohydrate structure and function. This Synpacts highlights recent advances in the synthesis and reactivity of Si-linked glycomimetics. First, a reductive intramolecular O → C silyl migration from C2 silyl ethers to C1 delivers 1,2-cis C–Si glycosides across diverse mono- and disaccharides with high anomeric control. A systematic variation of the reagent, counterion, solvent, and temperature delineates conditions that favor migration over competing elimination. Second, complementary anionic opening of glycal epoxides with aryl-substituted silicon nucleophiles furnishes 1,2-trans C–Si linkages cleanly while suppressing Peterson-type olefination. We further show that saccharide chirality can be relayed to silicon: monohydrosilanes undergo kinetic resolution under the transfer conditions, enabling access to configurationally defined silicon stereocenters. Beyond linkage construction, an oxidative ring contraction of anomeric metal/metalloid glycosides converts hexoses to pentose-derived γ-lactones under mild, stereospecific conditions, whereas β-anomers diverge to C2 ketones, revealing a stereoelectronic switch. Computations map the competition between (1,3)-retro-Brook transfer and Peterson elimination, identify a low-barrier Berry pseudorotation within a pentacoordinate oxasiletanide manifold that renders the transfer stereoretentive at silicon, and rationalize temperature-dependent pathways. Together, these results provide design rules and practical transformations for constructing Si-linked glycomimetics, installing silicon stereocenters, and editing carbohydrate ring size.
Publication History
Received: 11 November 2025
Accepted after revision: 19 January 2026
Article published online:
30 January 2026
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