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Knoevenagel Reaction of Unprotected Sugars

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Carbohydrates in Sustainable Development II

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 295))

Abstract

The Knoevenagel reaction of unprotected sugars was investigated in the 1950s using zinc chloride as promoter. The so-called Garcia Gonzalez reaction had been almost forgotten for 50 years, until the emergence of new water tolerant catalysts having Lewis acid behavior. The reaction was thus reinvestigated and optimal conditions have been found to prepare trihydroxylated furan derivatives from pentose or β-tetrahydrofuranylfuran from hexoses with non-cyclic β-keto ester or β-diketones. Other valuable compounds such as β-linked tetrahydrobenzofuranyl glycosides or hydroxyalkyl-3,3,6,6,-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione can be obtained using cyclic β-dicarbonylic derivatives. Apart from one report in the 1950s, the Knoevenagel reaction of unprotected carbohydrate in basic condition has been studied only in the mid-1980s to prepare C-glycosyl barbiturates from barbituric acids and, later on, from non-cyclic β-diketones, β-C-glycosidic ketones. The efficient method exploited to prepare such compounds has found an industrial development in cosmetics.

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Notes

  1. 1.

    In [92], the Authors might have inverted the compounds obtained from d-ribose or d-arabinose with those obtained from d-xylose. This error has been reproduced by Nagarapu et al. [94]. A debate of a hypothetic epimerization at C-1' has been engaged [91].

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  1. Institut de Chimie Moléculaire et des Matériaux d’Orsay, UMR 8182 Université Paris-Sud 11, 91405, Orsay Cedex, France

    Marie-Christine Scherrmann

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  1. Fac. Ciências, Depto. Química e Bioquímica, Universidade de Lisboa, Campo Grande, Lisboa, 1749-016, Portugal

    Amélia P. Rauter

  2. , EPFL ICMB LGSA, Swiss Federal Inst. of Technology, Bat BCH, Lausanne, 1015, Switzerland

    Pierre Vogel

  3. Labo. Chimie Organique (LCO), INSA Lyon, av. Albert Einstein 20, Villeurbanne CX, 69621, France

    Yves Queneau

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Scherrmann, MC. (2010). Knoevenagel Reaction of Unprotected Sugars. In: Rauter, A., Vogel, P., Queneau, Y. (eds) Carbohydrates in Sustainable Development II. Topics in Current Chemistry, vol 295. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2010_49

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