Palladium-Mediated Oxidative Homocoupling of Prop-2-ynyl Glycosides: Application Toward the Synthesis of Symmetrical Conjugated Sugar Diynes

Abstract

A palladium-catalyzed reaction has been applied toward the synthesis of divalent carbohydrate derivatives, which showed excellent lectin cross-linking abilities. The procedure, which involves copper(I) iodide and dichlorobis(triphenylphosphine)palladium(II)-catalyzed head-to-head coupling of prop-2-ynyl glycosides, is very efficient affording symmetrically conjugated carbohydrates containing 1,3-diynes in excellent yields. The reactions proceeded rapidly and efficiently at room temperature without the need for added oxidizing agents.

Key words

diynes - carbohydrates - oxidative homocoupling - palladium

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23

Recent observations showed that a catalytic amount of CuI (20 mol%, not optimized) gave similar results. However, the reactions were very slow without any copper(I) or in the presence of (Ph₃P)₄Pd. The reactions did not proceed with copper(I) alone under nitrogen.