654
3
Chemical Glycosylation Reactions
transglycosylation products was found to be independent of the anomeric ratio of the donor.
per-O-Acylated propargyl glycosides did not give transglycosylation products. A possible reaction pathway to the generation of an intermediate oxocarbenium ion, based on the
alkynophilicity of gold catalysts, was advanced by the authors ( > Scheme 88). Coordination
of AuCl 3 to the glycosyl donor 518 would be followed by formation of the cyclopropyl gold
carbene intermediate (520) that could evolve to intermediate 521, which would lead to oxocarbenium ion 522, and alkenyl gold complex 523. The latter upon protodemetalation will
generate AuCl 3 and cyclopropanone 525 via intermediate 524.
Acknowledgements
The author thanks the Dirección General de Enseñanza Superior (Grant CTQ2006-15279C03-02) for financial support.
References
1. Paulsen H (1982) Angew Chem Int Ed Engl
21:155
2. Schmidt RR (1986) Angew Chem Int Ed Engl
25:212
3. Paulsen H (1990) Angew Chem Int Ed Engl
29:823
4. Toshima K, Tatsuta K (1993) Chem Rev 93:1503
5. Schmidt RR (1986) Angew Chem Int Ed Engl
25:212
6. Boons GJ (1996) Tetrahedron 52:1095
7. Boons GJ (1996) Contemp Org Synth 3:173
8. Davis BG (2000) J Chem Soc Perkin Trans 1
2137
9. Demchenko AV (2005) Lett Org Chem 2:580
10. Fraser-Reid B, Konradsson P, Mootoo DR,
Udodong U (1988) J Chem Soc Chem Commun
823
11. Michael A (1879) Am Chem J 1:305
12. Fraser-Reid B, Udodong UE, Wu Z, Ottoson H,
Merrit JR, Rao CS, Roberts C, Madsen R (1992)
Synlett 927
13. Mootoo DR, Date V, Fraser-Reid B (1988)
J Chem Soc Chem Commun 1462
14. Mootoo DR, Fraser-Reid B (1986) J Chem Soc
Chem Commun 1570
15. Baldwin JE (1976) J Chem Soc Chem Commun
734
16. Mootoo DR, Date V, Fraser-Reid B (1988) J Am
Chem Soc 110:2662
17. Lemieux RU, Morgan AR (1965) Can J Chem
43:2190
18. Goodman L (1967) Adv Carbohydr Chem
Biochem 22:109
19. Mootoo DR, Konradsson P, Udodong U,
Fraser-Reid B (1988) J Am Chem Soc 110:
5583
20. Konradsson P, Mootoo DR, McDevitt RE,
Fraser-Reid B (1990) J Chem Soc Chem Commun 270
21. Veeneman GH, van Boom JH (1990) Tetrahedron Lett 31:275
22. Veeneman GH, van Leeuwen SH, van Boom JH
(1990) Tetrahedron Lett 31:1331
23. Friesen RW, Danishefsky SJ (1989) J Am Chem
Soc 111:6656
24. Barrena MI, Echarri R, Castillón S (1996) Synlett 675
25. Cheung MK, Douglas NL, Hinzen B, Ley SV,
Pannecoucke X (1997) Synlett 257
26. Hashimoto S, Sakamoto H, Honda T, Ikegami S
(1997) Tetrahedron Lett 38:5181
27. Hashimoto S, Sakamoto H, Honda T, Abe H,
Nakamura S, Ikegami S (1997) Tetrahedron Lett
38:8969
28. Mukaiyama T, Chiba H, Funasaka S (2002)
Chem Lett 392
29. Chiba H, Funasaka S, Kiyota K, Mukaiyama T
(2002) Chem Lett 746
30. Chiba H, Funasaka S, Mukaiyama T (2003) Bull
Chem Soc Jpn 76:1629
31. Demchenko AV, Kamat MN, De Meo C (2003)
Synlett 1287
32. Kamat MN, Demchenko AV (2005) Org Lett
7:3215
33. Bongat AFG, Kamat MN, Demchenko AV
(2007) J Org Chem 72:1480
3
Chemical Glycosylation Reactions
transglycosylation products was found to be independent of the anomeric ratio of the donor.
per-O-Acylated propargyl glycosides did not give transglycosylation products. A possible reaction pathway to the generation of an intermediate oxocarbenium ion, based on the
alkynophilicity of gold catalysts, was advanced by the authors ( > Scheme 88). Coordination
of AuCl 3 to the glycosyl donor 518 would be followed by formation of the cyclopropyl gold
carbene intermediate (520) that could evolve to intermediate 521, which would lead to oxocarbenium ion 522, and alkenyl gold complex 523. The latter upon protodemetalation will
generate AuCl 3 and cyclopropanone 525 via intermediate 524.
Acknowledgements
The author thanks the Dirección General de Enseñanza Superior (Grant CTQ2006-15279C03-02) for financial support.
References
1. Paulsen H (1982) Angew Chem Int Ed Engl
21:155
2. Schmidt RR (1986) Angew Chem Int Ed Engl
25:212
3. Paulsen H (1990) Angew Chem Int Ed Engl
29:823
4. Toshima K, Tatsuta K (1993) Chem Rev 93:1503
5. Schmidt RR (1986) Angew Chem Int Ed Engl
25:212
6. Boons GJ (1996) Tetrahedron 52:1095
7. Boons GJ (1996) Contemp Org Synth 3:173
8. Davis BG (2000) J Chem Soc Perkin Trans 1
2137
9. Demchenko AV (2005) Lett Org Chem 2:580
10. Fraser-Reid B, Konradsson P, Mootoo DR,
Udodong U (1988) J Chem Soc Chem Commun
823
11. Michael A (1879) Am Chem J 1:305
12. Fraser-Reid B, Udodong UE, Wu Z, Ottoson H,
Merrit JR, Rao CS, Roberts C, Madsen R (1992)
Synlett 927
13. Mootoo DR, Date V, Fraser-Reid B (1988)
J Chem Soc Chem Commun 1462
14. Mootoo DR, Fraser-Reid B (1986) J Chem Soc
Chem Commun 1570
15. Baldwin JE (1976) J Chem Soc Chem Commun
734
16. Mootoo DR, Date V, Fraser-Reid B (1988) J Am
Chem Soc 110:2662
17. Lemieux RU, Morgan AR (1965) Can J Chem
43:2190
18. Goodman L (1967) Adv Carbohydr Chem
Biochem 22:109
19. Mootoo DR, Konradsson P, Udodong U,
Fraser-Reid B (1988) J Am Chem Soc 110:
5583
20. Konradsson P, Mootoo DR, McDevitt RE,
Fraser-Reid B (1990) J Chem Soc Chem Commun 270
21. Veeneman GH, van Boom JH (1990) Tetrahedron Lett 31:275
22. Veeneman GH, van Leeuwen SH, van Boom JH
(1990) Tetrahedron Lett 31:1331
23. Friesen RW, Danishefsky SJ (1989) J Am Chem
Soc 111:6656
24. Barrena MI, Echarri R, Castillón S (1996) Synlett 675
25. Cheung MK, Douglas NL, Hinzen B, Ley SV,
Pannecoucke X (1997) Synlett 257
26. Hashimoto S, Sakamoto H, Honda T, Ikegami S
(1997) Tetrahedron Lett 38:5181
27. Hashimoto S, Sakamoto H, Honda T, Abe H,
Nakamura S, Ikegami S (1997) Tetrahedron Lett
38:8969
28. Mukaiyama T, Chiba H, Funasaka S (2002)
Chem Lett 392
29. Chiba H, Funasaka S, Kiyota K, Mukaiyama T
(2002) Chem Lett 746
30. Chiba H, Funasaka S, Mukaiyama T (2003) Bull
Chem Soc Jpn 76:1629
31. Demchenko AV, Kamat MN, De Meo C (2003)
Synlett 1287
32. Kamat MN, Demchenko AV (2005) Org Lett
7:3215
33. Bongat AFG, Kamat MN, Demchenko AV
(2007) J Org Chem 72:1480