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Synlett 2005(17): 2641-2642  
DOI: 10.1055/s-2005-917110
LETTER
© Georg Thieme Verlag Stuttgart · New York

Direct Synthesis of Glycidic Bicyclic Scaffolds in Water without Protecting Groups

Barbara La Ferla*a, Francisco Cardonaa, Ines Perdigãoa,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
Further Information

Publication History

Received 8 August 2005
Publication Date:
05 October 2005 (online)

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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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8

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).

9

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).