Application of the Indium-Mediated Allylation Reaction: Synthesis of 3-Deoxy-2-Uloses

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Mini symposium: Glycobiology at the LUMC and beyond

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Application of the Indium-Mediated Allylation Reaction: Synthesis of 3-Deoxy-2-Uloses

Manuel Gintner 1 , Christian Denner 1 , Christoph Schmölzer 1 , Michael Fischer 1 , Peter Frühauf 2 , Hanspeter Kählig 1 , Walther Schmid 1

1 Institute of Organic Chemsitry, University Of Vienna, Vienna, Austria, 2 Institute of Analytical Chemistry, University of Vienna, Vienna, Austria

The indium-mediated allylation reaction is a powerful tool for the elongation of carbohydrates since it can be performed in aqueous media under mild conditions [1,2]. We utilized this reaction in the synthesis of carbohydrate scaffolds containing the 3-deoxy-2-ulose motif, a barely investigated compound class [3]. The stereoselective outcome can be controlled by the presence or absence of a chelating group in α-position to the reacting carbonyl function as we verify on two model substrates [4,5]. Our approach towards the synthesis of 3-deoxy-D glycero-D-galacto-2-nonulose - the ketose analogue of widely distributed 2-keto-3-deoxy-D-glycero-D-galacto-nonoic acid (KDN) - is accompanied by demanding epimer separation which has been tackled by the introduction of an UV-active group attached to the allyl building block facilitating detection using HPLC. Synthetic as well as experimental details will be presented.

Scheme: Application of the indium-mediated allylation reaction in the synthesis of 3-deoxy-2-uloses and tackling of demanding epimer separation.

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Paquette, L. A. Evaluation of Chelation Effects Operative during Diastereoselective Addition of the Allylindium Reagent to 2- and 3-Hydroxycyclohexanones in Aqueous, Organic, and Mixed Solvent Systems. Synthesis 2003, 5, 765.

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