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Exploiting non-covalent interactions in selective carbohydrate synthesis

Abstract

Non-covalent interactions (NCIs) are a vital component of biological bond-forming events, and have found important applications in multiple branches of chemistry. In recent years, the biomimetic exploitation of NCIs in challenging glycosidic bond formation and glycofunctionalizations has attracted significant interest across diverse communities of organic and carbohydrate chemists. This emerging theme is a major new direction in contemporary carbohydrate chemistry, and is rapidly gaining traction as a robust strategy to tackle long-standing issues such as anomeric and site selectivity. This Review thus seeks to provide a bird’s-eye view of wide-ranging advances in harnessing NCIs within the broad field of synthetic carbohydrate chemistry. These include the exploitation of NCIs in non-covalent catalysed glycosylations, in non-covalent catalysed glycofunctionalizations, in aglycone delivery, in stabilization of intermediates and transition states, in the existence of intramolecular hydrogen bonding networks and in aggregation by hydrogen bonds. In addition, recent emerging opportunities in exploiting halogen bonding and other unconventional NCIs, such as CH–π, cation–π and cation–n interactions, in various aspects of carbohydrate chemistry are also examined.

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Fig. 1: Thiourea-catalysed glycosylations of glycals and trichloroacetimidates.
Fig. 2: (Thio)urea-catalysed Koenigs–Knorr glycosylation, strain release glycosylation and site-selective functionalization.
Fig. 3: Chiral phosphoric acid and non-thiourea hydrogen bonding-catalysed glycosylations and glycofunctionalizations.
Fig. 4: Non-hydrogen bonding non-covalent-catalysed glycosylations and site-selective functionalizations.
Fig. 5: Hydrogen bond-mediated aglycone delivery (HAD).
Fig. 6: Stabilization of intermediates and transition states by non-covalent interactions.
Fig. 7: The influences of non-covalent intramolecular networks on glycosylation reactivity and selectivity.
Fig. 8: Aggregation of saccharides by HB and its effect on reactivity and selectivity.

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Acknowledgements

The author acknowledges Fonds der Chemischen Industrie for generous research funding through a Liebig fellowship. The Boehringer Ingelheim Foundation is also gratefully acknowledged for the strong funding support of the exploitation of non-covalent interactions in carbohydrate chemistry through the Plus 3 Perspectives Programme. Further personnel funding through the Alexander von Humboldt Foundation and the Max Planck Society is acknowledged. C. Xu and V. U. B. Rao are gratefully acknowledged for their pioneering experimental contributions related to catalytic glycosylations that capitalize on non-covalent interactions as the activation mode in the author’s research group. H. Waldmann is greatly acknowledged for generous support and mentorship. The Max Planck Institute of Molecular Physiology and the Faculty of Chemistry and Chemical Biology of the Technische Universität Dortmund are also acknowledged for infrastructural and personnel support. This Review is dedicated to the memory of Professor Dieter Enders. The author thanks the anonymous reviewers for their constructive and thought-provoking comments, and apologizes to colleagues whose work was not cited due to selected coverage and space constraints.

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Correspondence to Charles C. J. Loh.

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Glossary

Aglycone delivery

Conventionally an intramolecular synthetic strategy known as intramolecular aglycone delivery, used to dictate a 1,2-cis outcome from a two-step tethering–glycosylation sequence.

Site selectivity

A special case of chemoselectivity describing the differentiated reactivity among the similar functional groups in different chemical (often chiral) environments.

Anomeric selectivity

A term specific to carbohydrate chemistry that describes the diastereoselectivity at the anomeric centre upon the formation of a glycosidic bond.

Anomeric configuration

The stereochemical relationship between the anomeric centre and the configuration of the most distant stereogenic centre.

Catalyst control

The selectivity outcome of a reaction is determined by the Curtin–Hammett principle, through the difference in the energies of the catalyzed transition states leading to two or more stereoisomers.

Regioselectivity

The selective production of one structural isomer among many. Often used synonymously with ‘site selectivity’ in carbohydrate chemistry.

Kinetic control

The selectivity outcome of a reaction which is primarily determined by the rate of product formation.

Substrate control

Effectively the opposite of catalyst control. The selectivity of a reaction is defined by the information (perhaps chiral) inherent to the substrate and is not easily overridden.

Mesoscale inhomogeneity

A concept used to describe the formation of solute-containing clusters on the order of 100 nm and larger in the presence of solvent molecules.

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Loh, C.C.J. Exploiting non-covalent interactions in selective carbohydrate synthesis. Nat Rev Chem 5, 792–815 (2021). https://doi.org/10.1038/s41570-021-00324-y

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