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Synlett 2004(2): 0225-0230  
DOI: 10.1055/s-2003-44988
LETTER
© Georg Thieme Verlag Stuttgart · New York

Sc(OTf)3 as Efficient Catalyst for Aryl C-Glycoside Synthesis

Akimi Ben, Takahito Yamauchi, Takashi Matsumoto, Keisuke Suzuki*
Department of Chemistry, Tokyo Institute of Technology and CREST-JST Agency, 2-12-1, O-okayama, Meguro-ku, Tokyo 152-8551, Japan
Fax: +81(3)57342788; e-Mail: ksuzuki@chem.titech.ac.jp;
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Publikationsverlauf

Received 10 November 2003
Publikationsdatum:
08. Dezember 2003 (online)

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Abstracts

Sc(OTf)3 was found to be an efficient catalyst for the C-glycosylation of phenols. Reactions of various functionalized phenols and glycosyl acetates, including an azido-bearing one, are achieved by using a catalytic amount of Sc(OTf)3 (10 mol% for neutral sugars or 50 mol% for an azido sugar) under mild conditions.

Key words

aryl C-glycosides - O→C-glycoside rearrangement - scandium triflate - catalysis - ravidomycin

    References

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10

This work was presented at the 83rd Annual Meeting of the Chemical Society of Japan, March 2003, Tokyo, Abstract 2D-1-38.

11

The α-isomer was used for this study. Synthesis of 2 will be reported elsewhere.

13

Selected data of 1H NMR, 13C NMR, NOE and HMBC are shown below (Figure [2] ).

14

Experimantal procedure as follows: To a stirred mixture of Sc(OTf)3 (210 mg, 0.427 mmol; Aldrich, 99.995%), phenol 3 (417 mg, 1.28 mmol), powdered Drierite® (2.6 g) in 1,2-dichloroethane (15 mL), was added acetate 2 (361 mg, 0.878 mmol) in 1,2-dichloroethane (8 mL) at -30 °C. After the temperature was gradually raised to 12 °C during 0.5 h, the mixture was poured into sat. aq NaHCO3 solution. After filtration through a Celite pad, the products were extracted with EtOAc (3×), and the combined organic extracts were washed with brine, and dried over Na2SO4. Removal of the solvents in vacuo and purification by silica-gel column chromatography (hexane/EtOAc = 5:1) afforded C-glycoside β-4 as white powder (462 mg, 78%).

15

Typical experimental procedure for the aryl C-glycosylation of neutral sugars is described for the reaction of phenol 3 and glycosyl acetate 5a: To a stirred mixture of Sc(OTf)3 (6.7 mg, 14 µmol), phenol 3 (87.7 mg, 0.269 mmol), powdered Drierite® (403 mg) in 1,2-dichloroethane (1.5 mL), was added acetate 5a (49.8 mg, 0.134 mmol) in 1,2-dichloroethane (1.0 mL) at -30 °C. After the temperature was gradually raised to -10 °C during 1.0 h, the reaction was quenched with sat. aq NaHCO3 solution. After filtration through a Celite pad, the products were extracted with EtOAc (3×), and the combined organic extracts were washed with brine, and dried over Na2SO4. Removal of the solvents in vacuo and purification on silica-gel preparative TLC (hexane/acetone = 2:1) afforded C-glycoside 6a as white powder (75.9 mg, 89%).