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Turnbull, W. B.; Fascione, M. A.; Stalford, S. A., Science of Synthesis, (2007) 29, 965.
Glycosyl phosphorothioates may also be synthesized by anomeric S-phosphorylation (Scheme 43). Thus, sulfenyl bromide 135 (R1 = Br) reacts with the nucleophilic H-phosphonate 136 (R2 = H; X = O) in benzene (Method A) to give the phosphorothioate 137 (X = O) in a modest yield.[133] Alternatively, the glycosyl thiol 135 (R1 = H) reacts under basic conditions (Method B, using NaOEt) with the phosphorochloridate 136 (R2 = Cl; X = O) to give the same product.[133] This latter type of approach is the only route (Method C, using Et3N as the base) currently available for synthesizing the S-glycosyl phosphorothioselenoate 137 (X = Se) and related compounds free from their Se-glycosyl isomers.[134]
Meeeee 88 Meeeeeeee ee Meeeeeee Meeeeeeeeeeeeeeeeeeeeee ee Meeeeeee M-Meeeeeeeeeeeeee[888,888]
Meeeeeeeeeee Meeeeeeee
8,8-Meeeeeee-8-eeeeee-8-M-(8,8,8,8-eeeee-M-eeeeee-β-M-eeeeeeeeeeeeee)-8-eeee-8,8,8-eeeeeeeeeeeeeeeeee (888; M = Me):[888]
Meeeee M: M eeee ee eee eeeeeeeeeee 888 (M8 = M; 8.8 e, 8.88 eeee), eee eeeeeeeeeeeeeeeeeeeeeeeee 888 (M8 = Me; M = Me; 8 e, 8.88 eeee), eee Me8M (8.8 e, 8.88 eeee) ee eeeeeee (88 eM) (MMMMMMM: eeeeeeeeee) eee eeeeeee eee 88 e ee ee. Mee eeeeeee eee eeeeee eeee M8M, eeeee (MeMM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeeeeeee [MMe8 (MMMMMMM: eeeee)/Me8M/eeeeeeeee eeeee] ee eeee eee eeeee eeeeeeee ee eeeeeeeee eeeeeee; eeeee: 8.8 e (88%); ee 888–888°M.
References
[133] | Meeeeeeee, M.; Meeeeeeee, M.; Meeeee, M., Meeeeeeeeee, (8888) 88, 888. |
[134] | Meeeeeeee, M.; Meeeee-Meeeee, M.; Meeeeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |