Cesium Trifluoroacetate or Silver Oxide Mediated Acyl Migration for the Construction of Disaccharide Building Blocks

Abstract

A convenient method for the selective differentiation of the 2-OH and 3-OH of pyranosides, based on the CsO₂CCF₃- or Ag₂O-mediated acyl migration, has been established. The 2-OH and 3-OH can be sequentially glycosylated by the desired carbohydrate generating disaccharides of biological interest. A mechanism involving either acid- or base-assisted acyl migration is proposed.

Key words

ABO blood group antigens - silver oxide - cesium tri­fluoroacetate - acyl migration - migration mechanisms

References and Notes

• 1a Nicolaou KC. Mitchell HJ. Angew. Chem. Int. Ed.  2001,  40:  1576 
• 1b Koeller KM. Wong C.-H. Chem. Rev.  2000,  100:  4465 
• 1c Lindhorst TK. Essentials of Carbohydrate Chemistry and Biochemistry   Wiley-VCH; Weinheim: 2003. 
• 2 Feizi T. Nature (London)  1985,  314:  53 
• 3a Lemieux RU. Driguez H. J. Am. Chem. Soc.  1975,  97:  4069 
• 3b Love KR. Seeberger PH. J. Org. Chem.  2005,  70:  3168 
• 4 Yi W. Shao J. Zhu L. Li M. Singh M. Lu Y. Lin S. Li H. Ryu K. Shen J. Guo H. Yao Q. Bush CA. Wang PG. J. Am. Chem. Soc.  2005,  127:  2040 
• 5a Gangadharmath UB. Demchenko AV. Synlett  2004,  2191 
• 5b David S. In Preparative Carbohydrate Chemistry   Hanessian S. Marcel Dekker Inc.; New York: 1997.  p.69-83  
• 5c Gridley JJ. Osborn HMI. Suthers WG. Tetrahedron Lett.  1999,  40:  6991 
• 5d Osborn HMI. Brome VA. Harwood LM. Suthers WG. Carbohydr. Res.  2001,  332:  157 
• 6a Garegg PJ. Pure Appl. Chem.  1984,  56:  845 
• 6b Jiang L. Chan T.-H. J. Org. Chem.  1998,  63:  6035 
• 7 Wang C.-C. Lee J.-C. Luo S.-Y. Fan H.-F. Pai C.-L. Yang W.-C. Lu L.-D. Hung S.-C. Angew. Chem. Int. Ed.  2002,  41:  2360 
• 8b Gridley JJ. Hacking AJ. Osborn HMI. Spackman DG. Tetrahedron  1998,  54:  14925 
• 9 Wang H. She J. Zhang L.-H. Ye X.-S. J. Org. Chem.  2004,  69:  5774 
• 10 Haines AH. Adv. Carbohydr. Chem. Biochem.  1976,  33:  11 
• 11 Bourne EJ. Huggard AJ. Tatlow JC. J. Chem. Soc.  1953,  735 
• 12 Chittenden GJF. Buchanan JG. Carbohydr. Res.  1969,  11:  379 
• 13 Qiu D. Schmidt RR. Liebigs Ann. Chem.  1992,  217 
• 14a Li J. Wang J. Czyryca PG. Chang H. Osak TW. Evanson R. Chang C.-WT. Org. Lett.  2004,  6:  1381 
• 14b

  Wang, J.; Li, J.; Chang, C.-W. T. unpublished results

15

Acyl Migration Using Ag ₂ O; General Procedure. A solution of starting material (0.12 mmol) and TBAI (4.2 mg, 0.012 mmol), Ag₂O (0.12 mmol) in anhyd DMF (5 mL) was stirred at the indicated temperature. The reaction was monitored by TLC. When the side product appeared, the reaction mixture was subsequently filtered then concentrated. The filtrate was subject to flash column chromatography to yield the desired product. The unreacted starting material was recovered.

16

Acyl Migration Using CsO ₂ CCF ₃ ; General Procedure. A mixture of starting material (0.20 mmol), CsO₂CCF₃ (0.20 mmol), and TBAI (8 mg, 0.02 mmol) in anhyd DMF (10 mL) was stirred at the indicated temperature. The reaction was monitored by TLC. When the side product appeared, the reaction mixture was filtered then concentrated. The filtrate was subject to flash column chromatography to yield the desired product. The unreacted starting material was recovered.