Total synthesis of bidensyneosides A 2 and C: Remarkable protecting group effects in glycosylation

Tetrahedron

Volumn 60, Issue 42, 2004, Pages 9405-9415

  Gung, Benjamin W ^a   Fox, Ryan M ^a  

^a MIAMI UNIVERSITY   (United States)

Author keywords

Bidensyneosides; Glycosylation; Natural product; Protecting group effect; Total synthesis

Indexed keywords

3 DEOXYBIDENSYNEOSIDE C; ACETYLENE DERIVATIVE; BIDENS PARVIFLORA EXTRACT; BIDENSYNEOSIDE A2; BIDENSYNEOSIDE C; ESTER; GLUCOSIDE; NATURAL PRODUCT; NITRIC OXIDE; PLANT EXTRACT; UNCLASSIFIED DRUG;

ARTICLE; BIDENS PARVIFLORA; CHINESE MEDICINE; DRUG SYNTHESIS; GLYCOSYLATION; HISTAMINE RELEASE; MEDICINAL PLANT; PRIORITY JOURNAL; PROTECTION; STEREOCHEMISTRY;

BIDENS;

EID: 4544316345     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2004.08.012     Document Type: Article

References (22)

1. N.L. Wang, X.S. Yao, R. Ishii, and S. Kitanaka Chem. Pharm. Bull. 49 2001 938 942
2. N.L. Wang, X.S. Yao, R. Ishii, and S. Kitanaka Phytochemistry 62 2003 741 746
3. Garegg, P. J. Thioglycosides as glycosyl donors in oligosaccharide synthesis. In Advances in Carbohydrate Chemistry and Biochemistry, 1997; Vol. 52, pp 179-205.
4. Z.Y. Zhang, I.R. Ollmann, X.S. Ye, R. Wischnat, T. Baasov, and C.H. Wong J. Am. Chem. Soc. 121 1999 734 753
5. K. Burgess, and L.D. Jennings J. Am. Chem. Soc. 112 1990 7434 7436
6. K. Burgess, and L.D. Jennings J. Am. Chem. Soc. 113 1991 6129 6139
7. M. Schmidt, S.K. Chatterjee, B. Dobner, and P. Nuhn Chem. Phys. Lipids 114 2002 139 147
8. B. Fraserreid, U.E. Udodong, Z.F. Wu, H. Ottosson, J.R. Merritt, C.S. Rao, C. Roberts, and R. Madsen Synlett 1992 927 942
9. J.P. Marino, M.S. McClure, D.P. Holub, J.V. Comasseto, and F.C. Tucci J. Am. Chem. Soc. 124 2002 1664 1668
10. H. Hofmeister, K. Annen, H. Laurent, and R. Wiechert Angew. Chem. 96 1984 720 721
11. Brandsma, L. Preparative Acetylenic Chemistry, 2nd ed.; 1988; Elsevier: New York, Vol. 34.
12. A.J. Mancuso, and D. Swern Synthesis 1981 165 185
13. R.E. Ireland, and D.W. Norbeck J. Org. Chem. 50 1985 2198 2200
14. I. Nomura, and C. Mukai Org. Lett. 4 2002 4301 4304
15. B.M. Trost, J.L. Belletire, S. Godleski, P.G. McDougal, J.M. Balkovec, J.J. Baldwin, M.E. Christy, G.S. Ponticello, S.L. Varga, and J.P. Springer J. Org. Chem. 51 1986 2370 2374
16. P. Fugedi, and P.J. Garegg Carbohydr. Res. 149 1986 C9 C12
17. Fraser-Reid, B.; Madsen, R.; Campbell, A. S.; Roberts, C. S.; Merritt, J. R. Chemical synthesis of oligosaccharides. In Bioorganic Chemistry: Carbohydrates; Hecht, S. M., Ed.; Oxford University Press: New York, 1999; pp 89-133.
18. X.S. Ye, and C.H. Wong J. Org. Chem. 65 2000 2410 2431
19. K. Matsuoka, S.I. Nishimura, and Y.C. Lee Bull. Chem. Soc. Jpn 68 1995 1715 1720
20. W. Wang, and F. Kong J. Org. Chem. 63 1998 5744 5745
21. B.W. Gung, and G. Kumi J. Org. Chem. 68 2003 5956 5960
22. One reviewer has given another reasonable explanation regarding the outcome of glycosylation versus orthoester formation: 'The C2-acetate stabilized oxycarbenium ion may be attacked by the incoming nucleophile at either the acetate carbonyl carbon, thus leading to the orthoester product, or at the anomeric carbon, leading to the desired glycosylation. The observed differences (between observed products with C3-OTBS versus C3-OAc protected donors) may simply reflect subtle differences in the kinetics of the attacks at these two centers: the more sterically congested OTBS protected substrate (which also yields a more stable oxycarbenium ion that 'demands less' in terms of stabilization by the C2-acetate relative to the C3-OAc protected donor) may not favor orthoester formation, as this would require developing unfavorable interactions (between the methyl group of the C2 acetate and the TBS group) in the transition state. Similar unfavorable interactions may deter the TBS-protected system from adopting a ring conformation that is favorable to orthoester formation.'