Synthesis of 2,3-Unsaturated O- and N-Glycosides by HBF₄˙SiO₂-Catalyzed Ferrier Rearrangement of d-Glycals

Abstract

Fluoroboronic acid adsorbed on silica gel (HBF₄˙SiO₂) catalyzes the Ferrier rearrangement of per-O-acetylated glycals with alcohols and sulfonamides to give 2,3-unsaturated O- and N-glycosides in good to excellent yield and with high α-stereoselectivity.

Key words

glycosylations - green chemistry - Ferrier rearrangement - N-glycosylsulfonamides - O-glycosides

References and Notes

• 1 Arya DP. Quevillon S. Joseph R. Wei C.-Q. Gan Z. Parisien M. Sesmilo B. Redddy PT. Chen Z.-X. Durieux P. Laforce D. Campeau LC. Khadem S. Daroszewska M. Barnes ML. Pure Appl. Chem.  2005,  77:  163 
• 2 Chambers DJ. Evans GR. Fairbanks AJ. Tetrahedron: Asymmetry  2005,  16:  45 
• 3 Schmidt RR. Angerbauer R. Angew. Chem., Int. Ed. Engl.  1977,  16:  783 
• 4 Danishefsky SJ. Bilodeau MT. Angew. Chem., Int. Ed. Engl.  1996,  120:  13515 
• 5 Colinas PA. Bravo RD. Vullo D. Scozzafava A. Supuran CT. Bioorg. Med. Chem. Lett.  2007,  17:  5086 
• 6 Ferrier RJ. Prasad N. J. Chem. Soc. C.  1969,  570 
• 7 Klaffke W. Puddlo P. Springer D. Thiem J. Liebigs Ann. Chem.  1991,  509 
• 8 Grynkiewicz G. Priebe W. Zamojski A. Carbohydr. Res.  1979,  68:  33 
• 9 Tilve RD. Alexander MV. Khandekar AC. Samant SD. Kanetkar VR. J. Mol. Catal. A: Chem.  2004,  223:  237 
• 10 Yadav JS. Reddy BVS. Murthy CVSR. Kumar GM. Synlett  2000,  1450 
• 11 Babu BS. Balasubramanian KK. Tetrahedron Lett.  2000,  41:  1271 
• 12 Ronaldo NO. Filho JRF. Srivastava RM. Tetrahedron Lett.  2002,  43:  2141 
• 13 Swamy NR. Venkateswarlu Y. Synthesis  2002,  598 
• 14 Yadav JS. Reddy BVS. Reddy JSS. J. Chem. Soc., Perkin Trans. 1  2002,  2390 
• 15 Yadav JS. Reddy BVS. Reddy KB. Satyanarayana M. Tetrahedron Lett.  2002,  43:  7009 
• 16 Bettadaiah BK. Srinivas P. Tetrahedron Lett.  2003,  44:  7257 
• 17 Toshima K. Ishizuka T. Matsuo G. Nakata M. Konoshita M. J. Chem. Soc., Chem. Commun.  1993,  704 
• 18 López JC. Gómez AM. Valverde S. Fraser-Reid B.
  J. Org. Chem.  1995,  60:  3851 
• 19 Rafiee E. Tangestaninejad S. Habibi MH. Mirkhani V. Bioorg. Med. Chem. Lett.  2004,  14:  3611 
• 20 Koreeda M. Houston TA. Shull BK. Klemke E. Tuinman RJ. Synlett  1995,  90 
• 21 Pachamuthu K. Vankar YD. J. Org. Chem.  2001,  66:  7511 
• 22 Banik BK. Adler D. Nguyen P. Srivastava N. Heterocycles  2003,  61:  101 
• 23 Naik PU. Nara SJ. Harjani JR. Salunkhe MM.
  J. Mol. Catal. A: Chem.  2005,  234:  35 
• 24 Hotha S. Tripahi A. Tetrahedron Lett.  2005,  46:  4555 
• 25 Zhang G. Liu Q. Shi L. Wang J. Tetrahedron Lett.  2008,  64:  339 
• 26a Agarwal A. Rani S. Vankar YD. J. Org. Chem.  2004,  69:  6137 
• 26b Misra AK. Tiwari P. Agnithori G. Synthesis  2005,  260 
• 27 Sharma G. Kumar R. Chakraborti AK. Tetrahedron Lett.  2008,  49:  4272 
• 28 Kumar D. Kumar R. Chakraborti AK. Synthesis  2008,  1249 
• 29 Bandgar BP. Patil AV. Kamble VT. Totre JV. J. Mol. Catal. A: Chem.  2007,  273:  114 
• 30 Chakraborti AK. Gulhane R. Tetrahedron Lett.  2003,  44:  3521 
• 33 Colinas PA. Bravo RD. Org. Lett.  2003,  5:  4509 
• 34 Procopio A. Dalpozzo R. De Nino A. Maiuolo L. Nardi M. Oliverio M. Russo B. Carbohydr. Res.  2007,  342:  2125 
• 35 Sabesan S. Neira S. J. Org. Chem.  1991,  56:  5468 

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Experimental Procedure
To a solution of the glycal (0.5 mmol) and the nucleophile (2 equiv) in dry MeCN (4 mL), the catalyst was added at 40 ˚C. After stirring for the time indicated, the reaction was filtered and the solvent evaporated in vacuo. The residue was chromatographed on SiO₂ (eluent hexane-EtOAc) to afford the glycosides.
Preparation of HBF ₄ ˙SiO ₂
A magnetically stirred suspension of SiO₂ (13.4 g, 230-400 mesh) in Et₂O (37 mL) was treated with 40% aq HBF₄ (1.5 g) for 3 h. The mixture was concentrated and the residue dried under vacuum at 100 ˚C for 24 h to afford HBF₄˙SiO₂ (0.5 mmol g^-¹). [³0]

32

The ^¹H NMR (200 MHz) spectra of the glycosides confirmed the α-configuration of the products formed in the reactions by comparison with the literature data.