A mild and easy one-pot procedure for the synthesis of 2-deoxysugars from glycals

doi:10.1016/S0040-4039(00)01643-9

Tetrahedron Letters

Volume 41, Issue 47, 18 November 2000, Pages 9177-9180

https://doi.org/10.1016/S0040-4039(00)01643-9 Get rights and content

Abstract

Glycals can be converted into the corresponding 2-deoxysugars in good yields by treatment with N-iodosuccinimide in CH₃CN–H₂O 95:5 and removal of the iodide group using Na₂S₂O₄ in DMF/H₂O at room temperature. This method is easy to apply, sufficiently mild to allow the survival of acid-sensitive groups such as silyl and trityl ethers and less harmful to the environment than metal-based reactions.

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Acknowledgements

This work is the result of research supported by MURST (‘Progetto Giovani Ricercatori’ 1999). Mass and NMR spectra were recorded at the ‘Centro Interdipartimentale di Analisi Strumentale’, Università di Napoli ‘Federico II’. The assistance of the staff is gratefully acknowledged.

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Likewise, similar procedures also include the formation of 2-chloro-2-deoxyglycoside and subsequent radical dechlorination,9 as well as the preparation of 2-deoxy-2-phenylthio-glycoside followed by the reduction of Raney Nickel.10 Previous reports indicated that acid-catalyzed addition to glycals represents the most direct method that can be operated under various conditions, including hydrogen bromide,11 triphenylphosphine hydrogenbromide,12 Dowex-50 [H+] in the presence of LiBr,13 CeCl3·7H2O/NaI,14 LaCl3·7H2O/NaI,15 TMSOTf–NEt3,16 BCl3 (or BBr3),17 ceric ammonium nitrate,18 GaCl3,19 and Rhenium(V) [ReOCl3(SMe2)(OPPh3)].20 We recently applied microwave-assisted glycosylation of hex-1-en-3-uloses to synthesize α-2-deoxyulosides.21
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While the product distribution revealed that this reaction was very sensitive to the configuration of the 2-deoxy-2-iodopyranose, 2-iodopyranoid glycals could be obtained almost exclusively in good yields by employing a 3,4-O-isopropylidene as a cyclic bifunctional protecting group.42 C-1 iodoglycals 39 have been synthesized from 2-deoxy-2-halo-1-lithioglycals (Scheme 13).43,44 The C-1 iodoglycals have been utilized in a variety of organometallic coupling reactions.
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From glycals, 2-deoxy-1-thioglycosides were obtained as mixtures of α- and β-anomers by using cerium ammonium nitrate (CAN) as catalyst, although the 2,3-unsaturated enose was also formed, especially from the glucal configuration (Scheme 9). The resulting 2-deoxy-1-thioglycosides were used as glycosyl donors, leading exclusively to the 2-deoxy-1-glycosides.43 Reductive removal of groups at C-2 has been accomplished,44 among others, by the procedure of Barton and McCombie (see Section II.3).
This chapter describes the occurrence and synthesis of deoxy sugars. Several deoxy sugars, notably 2-deoxy-D-erythro-pentose (2-deoxy-D-ribose)—the sugar component of DNA, 6-deoxy-L-mannose (L-rhamnose), 6-deoxy-L-galactose (L-fucose), 6-deoxy-D-glucose (quinovose), and their derivatives, occur very widely in natural product. The iodo and bromo derivatives of monosaccharides can be reduced by a variety of reducing agents to afford the corresponding deoxy sugar. The more stable chloro derivatives can be reduced with Raney nickel. Selective reduction of a secondary chloride with respect to a primary chloride may be achieved if the reduction is performed in the presence of triethylamine. Mesylates or tosylates may be reduced directly or through the intermediate halides or epoxides. Epoxides are involved in the reduction of tosylates by lithium aluminum hydride or lithium triethyl borohydride. A general method for the synthesis of 2-deoxyaldoses utilizes a reaction sequence involving the formation and subsequent reduction of ketene dithioacetal intermediates.

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A mild and easy one-pot procedure for the synthesis of 2-deoxysugars from glycals

Abstract

Section snippets

Acknowledgements

Tetrahedron

Carbohydr. Res.

Angew. Chem., Int. Ed. Engl.