Iodine → HCID 90357938, compound

HRID 522178Notes

Reaction equation

HRID 522178 reaction equation
[I:1]I.[CH2:3]([O:10][C@H:11]1[C@@H:16]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C@H:15]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C@@H:14]([CH2:33][O:34][CH2:35][C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[O:13][C@@H:12]1[CH2:42][Hg]Cl)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1>C(Cl)Cl>[CH2:26]([O:25][C@H:15]1[C@H:16]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C@H:11]([O:10][CH2:3][C:4]2[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=2)[C@@H:12]([CH2:42][I:1])[O:13][C@@H:14]1[CH2:33][O:34][CH2:35][C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

4

Reactant 2

HCID 807IodineHCID 90358076HCID 90358076, compound

Product 1

HCID 90357938HCID 90357938, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Iodine (0.36 g, 14.4 mmol, 1.1 equiv) dissolved in dry DCM (20 mL) was added to a solution of (((2S,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)methyl)mercury(II) chloride (1.0 g, 12.9 mmol, 1.0 equiv) in dry DCM (30 mL). The reaction mixture was stirred at room temperature for 16 hours and then quenched with saturated aqueous sodium thiosulfate solution (50 mL). The biphasic mixture was separated and then the organic layer was washed with saturated aqueous sodium chloride solution (10 mL) and then with water (10 mL). The organic layer was then dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The material thus obtained was purified by silica gel chromatography, eluting with 30% EtOAc in petroleum ether, to give (2R,3R,4S,5S,6S)-3,4,5-tris(benzyloxy)-2-((benzyloxy)methyl)-6-(iodomethyl)tetrahydro-2H-pyran as a colorless oil (0.7 g, 82%). 1H NMR (300 MHz, CDCl3) δ 7.44-7.22 (m, 18H), 7.17 (dd, J=6.6, 3.0 Hz, 2H), 5.09 (d, J=11.3 Hz, 1H), 4.92-4.67 (m, 4H), 4.67-4.47 (m, 3H), 4.21 (dd, J=2.8, 1.1 Hz, 1H), 3.90 (t, J=9.5 Hz, 1H), 3.76 (dd, J=11.0, 1.9 Hz, 1H), 3.71-3.60 (m, 2H), 3.57 (t, J=6.9 Hz, 1H), 3.53-3.45 (m, 1H), 3.35-3.24 (m, 2H). ESI (M+H2O) 682.2; calc for C35H37IO5 664.2.

Workup

  1. customquenched with saturated aqueous sodium thiosulfate solution (50 mL)
  2. customThe biphasic mixture was separated
  3. washthe organic layer was washed with saturated aqueous sodium chloride solution (10 mL)
  4. dry with materialThe organic layer was then dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe material thus obtained
  8. customwas purified by silica gel chromatography
  9. washeluting with 30% EtOAc in petroleum ether

Sources & evidence

ORD record
ord-b741f24b34224b4d85efc75ac1efce55
Source dataset
uspto-grants-2016_05
Patent number
US09328134B2

Reaction notes

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