Iodine → HCID 10897111, compound

HRID 522182Notes

Reaction equation

HRID 522182 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]([CH2:25][O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[O:14][C@H:13]([CH2:34][Hg]Cl)[C@@H:12]1[OH:37])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1>C(Cl)Cl>[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]([CH2:25][O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[O:14][C@H:13]([CH2:34][I:1])[C@@H:12]1[OH:37])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

4

Reactant 2

HCID 807IodineHCID 14158192HCID 14158192, compound

Product 1

HCID 10897111HCID 10897111, compoundYield 81%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of iodine (3.36 g, 13.2 mmol, 1.2 equiv) in DCM (168 mL) was added to a solution of (((2S,3R,4R,5R,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-3-hydroxytetrahydro-2H-pyran-2-yl)methyl)mercury(II) chloride (7.5 g, 11.0 mmol, 1.0 equiv) in dry DCM (26 mL) under nitrogen atmosphere. The mixture was stirred for 16 hours and then the reaction was quenched with aqueous sodium thiosulfate solution (20 g in 50 mL water). The mixture was stirred until colorless, the layers were separated, and the organic layer was washed with saturated sodium chloride solution (75 mL) and then water (75 mL). The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The material thus obtained was then purified by silica gel chromatography, eluting with 15% EtOAc in petroleum ether, to give (2S,3R,4R,5R,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-2-(iodomethyl)tetrahydro-2H-pyran-3-ol as a colorless oil (5.1 g, 81%). 1H NMR (300 MHz, CDCl3) δ 7.40-7.20 (m, 15H), 4.65-4.49 (m, 6H), 4.12 (td, J=5.5, 2.9 Hz, 1H), 4.02 (ddd, J=8.3, 5.8, 2.5 Hz, 1H), 3.85 (dd, J=10.1, 6.0 Hz, 2H), 3.74 (dt, J=10.4, 5.1 Hz, 2H), 3.63 (t, J=3.8 Hz, 1H), 3.40 (dd, J=10.3, 5.8 Hz, 1H), 3.29 (dd, J=10.5, 8.5 Hz, 1H), 3.11 (d, J=9.2 Hz, 1H). ESI (M+23) 597.0; calc for C28H31IO5 574.1.

Workup

  1. customthe reaction was quenched with aqueous sodium thiosulfate solution (20 g in 50 mL water)
  2. stirringThe mixture was stirred until colorless, the layers
  3. customwere separated
  4. washthe organic layer was washed with saturated sodium chloride solution (75 mL)
  5. dry with materialThe organic phase was dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe material thus obtained
  9. customwas then purified by silica gel chromatography
  10. washeluting with 15% EtOAc in petroleum ether

Sources & evidence

ORD record
ord-a9c80fe00da144189673a725c2ae7e01
Source dataset
uspto-grants-2016_05
Patent number
US09328134B2

Reaction notes

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