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Stereoselective Synthesis of 2-Deoxy-β-glycosides Using Anomeric O-Alkylation/Arylation.
| Content Provider | Semantic Scholar |
|---|---|
| Author | Morris, William J. Shair, Matthew D. |
| Copyright Year | 2009 |
| Abstract | Anomeric O-alkylation/arylation is applied to the synthesis of 2-deoxy-β-glycosides. Treatment of lactols with NaH in dioxane followed by the addition of electrophiles leads to the formation of 2-deoxy-β-glycosides in high yield and high selectivity. The high β-selectivity observed here demonstrates a powerful stereoelectronic effect for the stereoselective formation of acetals under kinetic control. 2-Deoxy-β-glycosides are present in biologically active natural products such as the lomaiviticins, olivomycin A, OSW-1, and durhamycin. The stereoselective preparation of 2-deoxy-β-glycosides is difficult because substituents at C2 often serve as directing groups during the glycosylation event. The synthesis challenge posed by 2deoxy-β-glycosides coupled with their presence in nature has inspired a variety of approaches aimed at accessing these important glycosides. The most common methods involve the use of a heteroatom substituent at C2 of the glycosyl donor followed by its reductive removal after glycosylation. Other methods include the use of α1 (1) Toshima, K.; Tatsuta, K. Chem. Rev. 1993, 93, 1503. 2 (2) (a) Roush, W. R.; Bennett, C. E. J. Am. Chem. Soc. 1999, 121, 3541. (b) Blanchard, N.; Roush, W. R. Org. Lett. 2003, 5, 81. (c) Thiem, J.; Gerken, M. J. Org. Chem. 1985, 50, 954. (d) Ito, Y.; Ogawa, T. Tetrahedron Lett. 1987, 28, 2723. (e) Grewal, G.; Kaila, N.; Franck, R. W. J. Org. Chem. 1992, 57, 2084. (f) Preuss, R.; Schmidt, R. R. Synthesis 1988, 694. (g) Franck, R. W.; Marzabadi, C. H. J. Org. Chem. 1998, 63, 2197. (h) Nicolaou, K. C.; Ladduwahetty, T.; Randall, J. L.; glycosyl phosphites, displacement of α-glycosyl halides, palladium catalyzed glycosylation reactions, utilization of alkoxy-substituted anomeric radicals, 6 and the use of glycosyl imidates as glycosyl donors under oxidative conditions. 7 Chucholowski, A. J. Am. Chem. Soc. 1986, 108, 2466. (i) Perez, M.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 75. (j) Gervay, J.; Danishefsky, S. J. Org. Chem. 1991, 56, 5448. (k) Tavecchia, P.; Trumtel, M.; Veyrieres, A.; Sinay, P. Tetrahedron Lett. 1989, 30, 2533. (l) Wiesner, K.; Tsai, T. Y. R.; Jin, H. Helv. Chim. Acta 1985, 68, 300. 3 (3) (a) Pongdee, R.; Wu, B.; Sulikowski, G. A. Org. Lett. 2001, 3, 3523. (b) Hashimoto, S.; Yanagiya, Y.; Honda, T.; Ikegami, S. Chem. Lett. 1992, 1511. 4 (4) (a) Binkley, R. W.; Koholic, D.J. J. Org. Chem. 1989, 54, 3577. (b) Toshima, K.; Misawa, M.; Ohta, K.; Tatsuta, K.; Kinoshita, M. Tetrahedron Lett. 1989, 30, 6417. 5 (5) Zhou, M.; O'Doherty, G. A. J. Org. Chem. 2007, 72, 2485. 6 (6) (a) Crich, D.; Ritchie, T. J. J. Chem. Soc. Perkin Trans. I 1990, 945. (b) Kahne, D.; Yang, D.; Lim, J. J.; Miller, R.; Paguaga, E. J. Am. Chem. Soc. 1988, 110, 8716. 7 (7) Tanaka, H.; Yoshizawa, A.; Takahashi, T. Angew. Chem. Int. Ed. 2007, 46, 2505. dr 4:1 (α:β) 11 examples, 61–91%, dr 8:1–20:1 O BnO BnO OH OBn NaH, dioxane 23 °C |
| File Format | PDF HTM / HTML |
| DOI | 10.1002/chin.200920177 |
| Volume Number | 40 |
| Alternate Webpage(s) | https://dash.harvard.edu/bitstream/handle/1/7982717/Shair_StereoselectiveAnomeric.pdf?isAllowed=y&sequence=1 |
| Alternate Webpage(s) | https://dash.harvard.edu/bitstream/handle/1/7982717/Shair_StereoselectiveAnomeric.pdf?sequence=1 |
| Alternate Webpage(s) | https://doi.org/10.1002/chin.200920177 |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
