Ozone → HCID 67006224, compound

HRID 1047513Notes

Reaction equation

HRID 1047513 reaction equation
[C:1]([Si:5]([O:8][CH:9]([CH2:13][CH2:14][CH:15]1[CH:24]([S:25]([C:28]2[CH:33]=[CH:32][C:31]([Cl:34])=[CH:30][CH:29]=2)(=[O:27])=[O:26])[C:23]2[C:18](=[C:19]([F:36])[CH:20]=[CH:21][C:22]=2[F:35])[O:17][CH2:16]1)[CH2:10][CH:11]=C)([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].[O:37]=[O+][O-].[BH4-].[Na+]>CO.C(Cl)Cl>[C:1]([Si:5]([CH3:6])([CH3:7])[O:8][CH:9]([CH2:13][CH2:14][CH:15]1[CH:24]([S:25]([C:28]2[CH:29]=[CH:30][C:31]([Cl:34])=[CH:32][CH:33]=2)(=[O:27])=[O:26])[C:23]2[C:18](=[C:19]([F:36])[CH:20]=[CH:21][C:22]=2[F:35])[O:17][CH2:16]1)[CH2:10][CH2:11][OH:37])([CH3:3])([CH3:2])[CH3:4]

Participants

5

Reactant 3

HCID 24823OzoneHCID 4311764Sodium borohydride2×HCID 67006120HCID 67006120, compound

Product 1

HCID 67006224HCID 67006224, compoundYield 50%

Reagents, catalysts & solvents 1

HCID 21226129Dichloromethane methanolSolvent

Procedure

A solution of tert-butyl-(1-{2-[4-(4-chloro-benzenesulfonyl)-5,8-difluoro-chroman-3-yl]-ethyl}-but-3-enyloxy)-dimethyl-silane (1.45 g, 2.60 mmol) in 1:1 MeOH/CH2Cl2 (25 mL) at −78° C. was purged with ozone until the blue color persisted. The reaction mixture was then purged with N2 for 5 min, treated with NaBH4 (300 mg, 7.8 mmol) portionwise and slowly warmed to ambient temperature. Over the next 4.5 h, 2 additional portions of NaBH4 (500 mg each) were added, and the reaction mixture was quenched with saturated aqueous NH4Cl and concentrated in vacuo. The residue was extracted with CH2Cl2 (3×). The combined organic extracts were washed saturated aqueous NaHCO3, dried over MgSO4 and concentrated in vacuo. Flash chromatography (5→40% EtOAc/Hex) afforded the title compound (730 mg, 50%): 1H NMR (CDCl3 400 MHz) δ 7.72 (dd, J=8.8, 1.5 Hz, 2H), 7.52 (dd, J=8.8, 1.5 Hz, 2H), 7.02 (m, 1H), 6.38 (m, 1H), 4.90 (dd, J=11.7, 2.2 Hz, 1H), 4.33 (d, J=12.4 Hz, 1H), 4.28 (s, 1H), 3.85 (m, 1H), 3.73-3.64 (m, 2H), 2.76 (m, 1H), 1.91 (br s, 1H), 1.71-1.22 (m, 6H), 0.80 (s, 4.5H), 0.79 (s, 4.5H), 0.03 (s, 3H), −0.04 (s, 3H).

Workup

  1. customThe reaction mixture was then purged with N2 for 5 min
  2. customthe reaction mixture was quenched with saturated aqueous NH4Cl
  3. concentrationconcentrated in vacuo
  4. extractionThe residue was extracted with CH2Cl2 (3×)
  5. washThe combined organic extracts were washed saturated aqueous NaHCO3
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-05eb0ec76dd7474ea673d92d0714404b
Source dataset
uspto-grants-2013_10
Patent number
US08569521B2

Reaction notes

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