反应详情

A solution of (((2S,3R,4S,5R,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-2-(iodomethyl)tetrahydro-2H-pyran-3-yl)oxy)(tert-butyl)dimethylsilane (4.0 g, 5.8 mmol, 1.0 equiv) in anhydrous triethyl phosphite (40 mL) was heated to 160° C. in a 100 mL sealed tube for 16 hours. The solvent was removed in vacuo and the resulting product was purified by silica gel chromatography, eluting with 30% EtOAc in petroleum ether, to give diethyl (((2S,3R,4S,5R,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-3-((tert-butyldimethylsilyl)oxy)tetrahydro-2H-pyran-2-yl)methyl)phosphonate as a pale yellow oil (3.36 g, 83%). 1H NMR (300 MHz, CDCl3) δ 7.37-7.22 (m, 13H), 7.06 (dd, J=6.6, 3.0 Hz, 2H), 4.90-4.72 (m, 3H), 4.67-4.61 (m, 1H), 4.49 (d, J=4.3 Hz, 1H), 4.46 (d, J=2.9 Hz, 1H), 4.40 (d, J=7.1 Hz, 1H), 4.17-4.03 (m, 4H), 3.93-3.85 (m, 1H), 3.77 (d, J=9.9 Hz, 1H), 3.72-3.61 (m, 3H), 3.55-3.47 (m, 1H), 2.27-2.13 (m, 2H), 1.29 (td, J=7.1, 1.2 Hz, 6H), 0.90 (s, 9H), 0.09 (s, 3H), 0.07 (s, 3H). ESI (M+1) 699.2; calc for C38H55O8PSi 698.3.

1. customsealed tube for 16 hours
2. customThe solvent was removed in vacuo
3. customthe resulting product was purified by silica gel chromatography
4. washeluting with 30% EtOAc in petroleum ether