Ozone → HCID 86701323, compound

HRID 1627049Notes

Reaction equation

HRID 1627049 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)[CH:13]=C[O:11][C@H:10]1[CH3:23])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([O-])(O)=[O:25].[Na+].O=[O+][O-].[BH4-].[Na+].CC([O-])=O.[Na+]>CO.C(Cl)Cl.O.CCOC(C)=O>[CH2:16]([O:15][C@H:14]([C@@H:9]([O:8][CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)[C@@H:10]([OH:11])[CH3:23])[CH2:13][OH:25])[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

Participants

10

Reactant 5

HCID 24823OzoneHCID 516892Sodium BicarbonateHCID 517045Sodium AcetateHCID 2734744ST50405674HCID 4311764Sodium borohydride

Product 1

HCID 86701323HCID 86701323, compoundYield 932.4%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of (2S,3S,4S)-3,4-bis(benzyloxy)-2-methyl-3,4-dihydro-2H-pyran (0.621 g, 2.00 mmol) and NaHCO3 (17.0 mg, 0.200 mmol) in MeOH (0.22 ml) and DCM (7 mL) was treated with ozone at −78° C. until the solution became light blue in color. The mixture was purged with nitrogen until colorless, diluted with MeOH (7 mL), and treated with a solution of NaBH4 (0.454 g, 12.0 mmol) and NaOAc (0.335 g, 4.08 mmol) in H2O (7 mL). The mixture was slowly warmed to room temperature and stirred for 12 h. The mixture was diluted with EtOAc and washed with H2O. The organic layer was separated and the aqueous layer was extracted with EtOAc. The combined organic phases were washed with brine, dried over MgSO4, filtered, and the filtrate concentrated. The crude residue was purified by flash chromatography (SiO2, hexanes/EtOAc gradient) to yield the title compound as a colorless oil (0.590 g, 93%): IR (neat) 3389, 2876, 1453, 1064, 733, 696 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.39-7.27 (m, 10H), 4.64 (s, 2H), 4.63 (s, 2H), 4.06-3.97 (m, 1H), 3.92-3.83 (m, 1H), 3.80-3.73 (m, 2H), 3.47 (dd, J=6.2, 4.3 Hz, 1H), 2.92 (d, J=4.9 Hz, 1H), 2.23 (dd, J=6.9, 4.9 Hz, 1H), 1.24 (d, J=6.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 137.91, 137.71, 128.69, 128.62, 128.23, 128.19, 128.09, 81.72, 79.53, 73.63, 72.78, 67.66, 61.45, 19.74; ESIMS m/z 339.2 ([M+Na]+).

Workup

  1. customThe mixture was purged with nitrogen until colorless,
  2. additiondiluted with MeOH (7 mL)
  3. washwashed with H2O
  4. customThe organic layer was separated
  5. extractionthe aqueous layer was extracted with EtOAc
  6. washThe combined organic phases were washed with brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationthe filtrate concentrated
  10. customThe crude residue was purified by flash chromatography (SiO2, hexanes/EtOAc gradient)

Sources & evidence

ORD record
ord-6725d45c15384d33b3c2913d39cc4b25
Source dataset
uspto-grants-2014_07
Patent number
US08785479B2

Reaction notes

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