Triethyl phosphite → HCID 87229753, compound

HRID 522184Notes

Reaction equation

HRID 522184 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:13]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:12][C@H:11]([CH2:32]I)[C@@H:10]1[O:34][Si:35]([C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:37])[CH3:36])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[P:42]([O:49]CC)([O:46][CH2:47][CH3:48])[O:43][CH2:44][CH3:45]>>[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:13]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:12][C@H:11]([CH2:32][P:42](=[O:49])([O:46][CH2:47][CH3:48])[O:43][CH2:44][CH3:45])[C@@H:10]1[O:34][Si:35]([C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:37])[CH3:36])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

3

Reactant 2

HCID 31215Triethyl phosphiteHCID 11858568HCID 11858568, compound

Product 1

HCID 87229753HCID 87229753, compoundYield 83%

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-26b022e3a4cb4ffea52ac5faacb3bdb9
Source dataset
uspto-grants-2016_05
Patent number
US09328134B2

Reaction notes

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