Synthesis of Spiro C-Arylglycoriboside via Pd(II)-Catalyzed
Spirocyclization

Ken-ichiro Awasaguchi; Masahiro Miyazawa; Ikuyo Uoya; Koichi Inoue; Koji Nakamura; Hajime Yokoyama; Hiroko Kakuda; Yoshiro Hirai

doi:10.1055/s-0030-1258560

LETTER

Synthesis of Spiro C-Arylglycoriboside via Pd(II)-Catalyzed Spirocyclization

Ken-ichiro Awasaguchi^a, Masahiro Miyazawa*^b, Ikuyo Uoya^b, Koichi Inoue^b, Koji Nakamura^b, Hajime Yokoyama^b, Hiroko Kakuda^c, Yoshiro Hirai*^a
^a Graduate School of Innovative Life Science, University of Toyama, 3190 Gohuku, Toyama 930-8555, Japan
Fax: +81(764)456115; e-Mail: hirai@adm.u-toyama.ac.jp;
^b Faculty of Science, Department of Chemistry, University of Toyama, 3190 Gohuku, Toyama 930-8555, Japan
e-Mail: miyazawa@sci.toyama-u.ac.jp;
^c Faculty of Medicine, Laboratory of Chemistry, University of Toyama, 2630 Sugitani, Toyama 930-0194, Japan

Abstract

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Abstract

Spiro C-arylglycoriboside was synthesized in 21 steps via Pd(II)-catalyzed spirocyclization as a key reaction. Hemiketal was obtained in 47% overall yield from cis-2-butene-1,4-diol and spirocyclized with PdCl₂(PhCN)₂ in dilute THF solution (0.01 M) to afford the 1,6-dioxaspiro[4.4]nonane skeleton in high yield. The spirocyclo adduct was transformed into spiro C-arylglycoriboside in five steps.

Key words

spiro compound - palladium - heterocycles - stereoselectivity - cyclization

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References

References and Notes

1 Perron F. Albizati KF. Chem. Rev. 1989, 89: 1617

For isolation, see:

2a Traxler P. Gruner J. Auden JA.
J. Antibiot. 1977, 30: 289

2b For structural characteri-zation, see: Traxler P. Frittz H. Richter WJ. Helv. Chim. Acta 1977, 60: 578

3a Barrett AGM. Pena M. Aillardsen JA. J. Org. Chem. 1996, 61: 1082

3b Denmark SE. Regens CS. Kobayashi T. J. Am. Chem. Soc. 2007, 129: 2774

4a Wu Q. Simons C. Synthesis 2004, 1533

4b Kool ET. Acc. Chem. Res. 2002, 35: 936

5 Yamamoto Y. Hashimoto T. Hattori K. Kikuchi M. Nishiyama H. Org. Lett. 2006, 8: 3565

6 Mori K. Kiyota H. Liebigs Ann. Chem. 1992, 989

7 Song ZJ. Zhao M. Desmond R. Devine P. Tschaen DM. Tillyer R. Frey L. Heid R. Xu F. Foster B. Li J. Reamer R. Volante R. Grabowski EJ. Dolling UH. Reider PJ. Okada S. Kato Y. Mano E. J. Org. Chem. 1999, 64: 9658

8 Miyazawa M. Hirose Y. Narantsetseg M. Yokoyama H. Yamaguchi S. Hirai Y. Tetrahedron Lett. 2004, 45: 2883

9 Yu W. Mei Y. Hua Z. Jin Z. Org. Lett. 2004, 6: 3217

10

The stereochemistry of 10a was confirmed unequivocally by single-crystal X-ray diffraction analysis.

11 Uenishi J. Vikhe YS. Kawai N. Chem. Asian J. 2008, 3: 473