Triethyl phosphite → HCID 131735507, compound

HRID 522179Notes

Reaction equation

HRID 522179 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]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C@@H:12]([CH2:31]I)[O:11][C@@H:10]1[CH2:33][O:34][CH2:35][C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1)[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]>>[CH2:24]([O:23][C@H:13]1[C@@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@H:9]([O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[C@@H:10]([CH2:33][O:34][CH2:35][C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[O:11][C@@H:12]1[CH2:31][P:42](=[O:49])([O:46][CH2:47][CH3:48])[O:43][CH2:44][CH3:45])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1

Participants

3

Reactant 2

HCID 31215Triethyl phosphiteHCID 90357938HCID 90357938, compound

Product 1

HCID 131735507HCID 131735507, compoundYield 70%

Procedure

A solution of (2R,3R,4S,5S,6S)-3,4,5-tris(benzyloxy)-2-((benzyloxy)methyl)-6-(iodomethyl)tetrahydro-2H-pyran (0.7 g, 0.75 mmol, 1.0 equiv) in anhydrous triethyl phosphite (9.0 mL) was heated to 160° C. in a 50 mL sealed tube for 16 hours. The solvent was removed using a Kugelrohr distillation setup, and the material thus obtained was purified by silica gel chromatography, eluting with 50% EtOAc in petroleum ether, to give diethyl (((2S,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)methyl)phosphonate as a pale yellow oil (0.5 g, 70%). 1H NMR (300 MHz, CDCl3) δ 7.52-6.98 (m, 20H), 4.77-4.66 (m, 1H), 4.63 (d, J=6.2 Hz, 2H), 4.60-4.42 (m, 6H), 4.16-3.99 (m, 4H), 3.91 (dq, J=8.1, 5.1, 3.9 Hz, 1H), 3.88-3.82 (m, 1H), 3.78 (q, J=4.0 Hz, 4H), 2.25-1.95 (m, 2H), 1.33-1.22 (m, 6H). ESI (M+1) 675.2; calc for C39H47O8P 674.3.

Workup

  1. customsealed tube for 16 hours
  2. customThe solvent was removed
  3. distillationa Kugelrohr distillation setup
  4. customthe material thus obtained
  5. customwas purified by silica gel chromatography
  6. washeluting with 50% EtOAc in petroleum ether

Sources & evidence

ORD record
ord-914366ad8fb74f8e98002bb55afe9c6a
Source dataset
uspto-grants-2016_05
Patent number
US09328134B2

Reaction notes

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