Efficient and β-Stereoselective Synthesis of Pyrazole C-Nucleosides

Abstract

3(5)-(β-d-Ribofuranosyl)pyrazole 1 and 3(5)-(2-deoxy-β-d-ribofuranosyl)pyrazole (2) were stereoselectively synthesized by cyclization of 1,2-diazafulvene intermediates obtained from 2,3,5-tri-O-benzyl-d-ribose (5) and 3,5-di-O-benzyl-2-deoxy-d-ribose (10), respectively.

pyrazole - C-nucleoside - β-anomer - stereoselective synthesis - diazafulvene

References

1a Shaban MAE. Nasr AZ. In Adv. Heterocycl. Chem.   Vol. 68:  Katritzky AR. Academic Press; San Diego: 1997.  p.259-277  

1b Shaban MAE. In Advances in Heterocyclic Chemistry   Vol. 70:  Katritzky AR. Academic Press; San Diego: 1998.  p.230-252  

1c Zhou J. Yang M. Schneller SW. Tetrahedron Lett.  2004,  45:  8233 

1d Watanabe KA. In The Chemistry of Nucleosides and Nucleotides   Vol. 3:  Towsend LB. Plenum; New York: 1994.  p.421-535  

1e Levy DE. Tang C. In The Chemistry of C-Glycosides   Pergamon; Oxford: 1995.  Chap. 1.

For reviews on the early work of C-nucleoside antibiotics, see:

2a Buchanan JG. Prog. Chem. Org. Nat. Prod.  1983,  44:  243 

2b Hacksell U. Daves GD. In Progress in Medicinal Chemistry   Vol. 22:  Ellis GP. West GB. Elsevier; Oxford: 1985.  p.1-65  

2c Popsavin M. Torovic L. Spaic S. Stankov S. Popsavin V. Tetrahedron Lett.  2000,  41:  5737 

3 Wu Q. Simons C. Synthesis  2004,  1533 ; and references cited therein

4a Rycroft AD. Singh G. Wightman RH. J. Chem. Soc., Perkin Trans. 1  1995,  2667 ; and references cited therein

4b Buchanan JG. Edgar AR. Power MJ. Williams GC. Carbohydr. Res.  1977,  55:  225 

4c Buchanan JG. Edgar AR. Power MJ. Williams GC. Nucleic Acid Res., Spec. Publ. No.1  1975,  s69 

4d Buchanan JG. Dunn AD. Edgar AR. Hutchison RJ. Power MJ. Williams GC. J. Chem. Soc., Perkin Trans. 1  1977,  1786 

4e Buchanan JG. Edgar AR. Hutchison RJ. Stobie A. Wightman RH. J. Chem. Soc., Perkin Trans. 1  1980,  2567 

5a Buchanan JG. Jumaah AO. Kerr G. Talekar RR. Wightman RH. J. Chem. Soc., Perkin Trans. 1  1991,  1077 

5b Buchanan JG. Edgar AR. Hutchison RJ. Stobie A. Wightman RH. J. Chem. Soc., Chem Commun.  1980,  237 

5c Buchanan JG. Stobie A. Wightman RH. Can. J. Chem.  1980,  58:  2624 

5d Buchanan JG. Stobie A. Wightman RH. J. Chem. Soc., Perkin Trans. 1  1981,  2374 

6a Harusawa S. Murai Y. Moriyama H. Imazu T. Ohishi H. Yoneda R. Kurihara T. J. Org. Chem.  1996,  61:  4405 

6b Araki L. Harusawa S. Suzuki H. Kurihara T. Heterocycles  2000,  53:  1957 

6c Harusawa S. Araki L. Kurihara T. J. Synth. Org. Chem. Jpn.  2003,  61:  682 

6d Araki L. Harusawa S. Yamaguchi M. Yonezawa S. Taniguchi N. Lilley DMJ. Zhao Z. Kurihara T. Tetrahedron Lett.  2004,  45:  2657 

6e Zhao Z. Mcleod A. Harusawa S. Araki L. Yamaguchi M. Kurihara T. Lilley DMJ. J. Am. Chem. Soc.  2005,  127:  5026 

6f The methodology using the cyclization of 1,3-diazafulvene generated in situ was recently extended to stereocontrolled synthesis of heterocyclic C-nucleosides (indole C-2 linked imidazole benzimidazole and 6-iodobenzimidazole): Guianvarc’h D. Fourrey J.-L. Dau M.-ETH. Guérineau V. Benhida R. J. Org. Chem.  2002,  67:  3724 

7a Grimmett MR. In Science of Synthesis   Vol. 12:  Neier R. Thieme; Stuttgart: 2002.  p.325-528  

7b Grimmett MR. In Imidazoles, In Comprehensive Heterocyclic Chemistry II   Vol. 3:  Katritzky AR. Rees CW. Scriven EF. Pergamon; Oxford: 1996.  p.77-220  

8a Stanovnik B. Svete J. In Science of Synthesis   Vol. 12:  Neier R. Thieme; Stuttgart: 2002.  p.15-225  

8b Grimmett MR. Iddon B. Heterocycles  1994,  37:  2087 

8c Elguero J. In Pyrazoles, In Comprehensive Heterocyclic Chemistry II   Vol. 3:  Katritzky AR. Rees CW. Scriven EF. Pergamon; Oxford: 1996.  p.1-75  

9a Barker R. Fletcher HG. J. Org. Chem.  1961,  26:  4605 

9b

We obtained 5 in an improved yield (76%) from d-ribose.

10a Effenberger F. Roos M. Ahmad R. Krebs A. Chem. Ber.  1991,  124:  1639 

10b

In our hands, the yield of 14 was improved to 99% by using NaH.

11 Tsunoda T. Otsuka J. Yamamiya Y. Itô S. Chem. Lett.  1994,  539 

12 Nishimura N. Banno M. Maki A. Nishiyama Y. Maeba I. Carbohydr. Res.  1998,  307:  211 

13 Erion MD. Rydzewski RM. Nucleosides Nucleotides  1997,  16:  315