Direct Synthesis of Glycidic Bicyclic Scaffolds in Water without Protecting Groups

Barbara La Ferla; Francisco Cardona; Ines Perdigão; Francesco Nicotra

doi:10.1055/s-2005-917110

LETTER

Direct Synthesis of Glycidic Bicyclic Scaffolds in Water without Protecting Groups

Barbara La Ferla*^a, Francisco Cardona^a, Ines Perdigão^a,b, Francesco Nicotra*^a
^a Department of Biotecnology and Bioscience, University of Milano Bicocca, Piazza della Scienza 2, 20126 Milano, Italy
Fax: +39(026)4483565; e-Mail: barbara.laferla@unimib.it;
^b Departamento de Quìmica e Bioquìmica, Faculdade de Ciências da Universidade de Lisboa, Ed. C8, 5° Piso, Campo Grande, 1749-016 Lisboa, Portugal

Abstract

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Abstract

Bicyclic scaffolds obtained from C-allyl glycosides have been synthesized in water, without the use of protecting groups. The scaffolds have been functionalized with different groups for chemoselective ligation.

Key words

bicyclic scaffold - darbohydrate - green chemistry - unprotected

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References

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General Procedure.
Primary alcohol (0.11 mmol) was dissolved in a sat. solution of NaHCO₃ (1.5 mL), and then KBr (0.1 equiv) and TEMPO (0.06 equiv) were added. The temperature was lowered to 15-18 °C and an aq solution of NaOCl (5%; 1 mL) was slowly added. The reaction was stirred at r.t. for 2 h then concentrated under reduced pressure. The products were purified by flash chromatography (EtOAc-MeOH-H₂O, 6:4:0.5).

Compound 9 (0.15 mmol) and Cs₂CO₃ (0.15 mmol) were dissolved in dry MeOH (1 mL). After 0.5 h the solution was added to a solution of compound 4a in dry MeOH-DMF 1:1 (2 mL) and left stirring at r.t. for 12 h. The reaction mixture was then concentrated under reduced pressure and the product was purified by flash chromatography (EtOAc-MeOH, 9:1).