A Comparative Study of the Influence of Protecting Groups on the Reactivity of chiro-Inositol Glycosyl Acceptors

Abstract

The influence of protecting groups on the reactivity of glycosyl acceptors has been investigated through a series of competitive glycosylation experiments using differently substituted C2 symmetric d-chiro-inositol derivatives. It has been shown that, for a given glycosyl donor, the protective group pattern effectively modulates the reactivity of these derivatives in the glycosylation ­reaction.

Key words

glycosylation - reactivity - stereoselectivity

References

• 2a Dwek RA. Chem Rev.  1996,  96:  683 
• 2b Varki A. Glycobiology  1993,  3:  97 
• 2c Carbohydrates in Chemistry and Biology   Vol. 1-4:  Ernst B. Hart GW. Sinaӱ P. Wiley-VCH; Weinheim: 2000. 
• 3a Paulsen H. Angew. Chem., Int. Ed. Engl.  1982,  21:  155 
• 3b Mootoo DR. Konradsson P. Udodong U. Fraser-Reid B. J. Am. Chem. Soc.  1988,  110:  5583 
• 4a Fraser-Reid B. Wu ZF. Andrews CW. Skowronski E. Bowen JP. J. Am. Chem. Soc.  1991,  113:  1434 
• 4b Douglas NL. Ley SV. Lücking U. Warriner SL. J. Chem. Soc., Perkin Trans. 1  1998,  51 
• 4c Zhang Z. Ollman IR. Ye X.-S. Wischnat R. Baasov T. Wong CH. J. Am. Chem. Soc.  1999,  121:  734 
• 5 For a review on one-pot glycosylation reactions, see: Koeller KM. Wong CH. Chem. Rev.  2000,  100:  4465 
• 6 See for example: Ritter TK. Mong K.-KT. Liu H. Nakatani T. Wong C.-H. Angew. Chem. Int. Ed.  2003,  42:  5221 ; and references cited therein
• 7a Huang X. Huang L. Wang H. Ye XS. Angew. Chem. Int. Ed.  2004,  43:  5221 
• 7b Xia J. Alderfer JL. Locke RD. Piskorz CF. Matta KL. J. Org. Chem.  2003,  68:  2752 
• 7c Xue J. Khaja D. Locke RD. Matta KL. Synlett  2004,  861 
• 8 Sinaӱ P. Pure Appl. Chem.  1978,  50:  1437 
• 9 Boons G.-J. Zhu T. Synlett  1997,  809 
• 10 Crich D. Dudkin V. J. Am. Chem. Soc.  2001,  123:  6819 
• 11a Khiar N. Martín-Lomas M. In Carbohydrate Mimics. Concepts and Methods   Chapleur Y. Wiley-VCH; Weinheim: 1998.  p.433-462  ; and references therein
• 11b Dietrich H. Espinosa JF. Chiara JL. Jiménez-Barbero J. León Y. Varela-Nieto I. Mato JM. Cano FH. Foces-Foces C. Martín-Lomas M. Chem.-Eur. J.  1999,  5:  320 
• 11c Martín-Lomas M. Flores-Mosquera M. Chiara JL. Eur. J. Org. Chem.  2000,  1547 
• 11d Reichardt N.-C. Martín-Lomas M. Angew. Chem. Int. Ed.  2003,  40:  4674 
• 12a Martín-Lomas M. Flores-Mosquera M. Khiar N. Eur. J. Org. Chem.  2000,  1539 
• 12b Martín-Lomas M. Khiar N. Garcia S. Koessler JL. Nieto PM. Rademacher TW. Chem.-Eur. J.  2000,  6:  3608 
• 12c Martín-Lomas M. Nieto PM. Khiar N. García S. Flores-Mosquera M. Poirot E. Angulo J. Muñoz JL. Tetrahedron: Asymmetry  2000,  11:  37 
• 13a Cid MB. Bonilla JB. Dumarcay S. Alonso F. Martín-Lomas M. Eur. J. Org. Chem.  2002,  881 
• 13b Bonilla JB. Muñoz-Ponce JL. Nieto PM. Cid MB. Martín-Lomas M. Eur. J. Org. Chem.  2002,  889 
• 13c Cid MB. Bonilla JB. Alfonso F. Martín-Lomas M. Eur. J. Org. Chem.  2003,  3505 
• 13d Cid MB. Alfonso F. Martín-Lomas M. Synlett  2003,  1370 
• 13e Cid MB. Alfonso F. Martín-Lomas M. Carbohydr. Res.  2004,  339:  2303 
• 14 Cid MB. Alfonso F. Martín-Lomas M. Chem.-Eur. J.  2005,  929 
• 15 Trichloroacetimidates 2 and 10 were prepared as described in: Kinzi W. Schmidt RR. Liebigs Ann. Chem.  1985,  1537 

1

Present address: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco 28049, Spain; fax [phone]; email: [e-mail].

16

Acceptor 5 was prepared from myo-inositol as reported in ref. 11d.

17

Cid, M. B.; Alfonso, F.; Martín-Lomas, M. unpublished results.

18

When d-chiro-inositol was submitted to standard basic benzylation conditions a complex mixture of products, from which 11 could not been isolated, was obtained. When the tetraol 27 precursor of 9 was treated with BnBr compound 28, resulting from benzylation of the axially oriented hydroxyl groups, was observed (Scheme [3] ).