Ethyl Acetate → HCID 67979386, compound

HRID 1770981Notes

Reaction equation

HRID 1770981 reaction equation
[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7]3([CH2:16][CH2:15][C:14]4([O:20][CH2:19][CH2:18][O:17]4)[CH2:13][CH2:12]3)[C:8]2=O)=[CH:4][CH:3]=1.[CH3:21][C:22]([S:25]([NH2:27])=[O:26])([CH3:24])[CH3:23].CCOC(C)=O>[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC.O>[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7]3([CH2:16][CH2:15][C:14]4([O:20][CH2:19][CH2:18][O:17]4)[CH2:13][CH2:12]3)[C:8]2=[N:27][S:25]([C:22]([CH3:24])([CH3:23])[CH3:21])=[O:26])=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 8857Ethyl AcetateHCID 3382465Tert-ButanesulfinamideHCID 67979501HCID 67979501, compound2×

Product 1

HCID 67979386HCID 67979386, compoundYield 69.3%

Reagents, catalysts & solvents 2

HCID 76524Titanium tetraethoxideCatalystHCID 962WaterSolvent

Procedure

6″-Bromodispiro[1,3-dioxolane-2,1′-cyclohexane-4′,2″-inden]-1″(3″H)-one (Intermediate 71, 320 mg, 0.95 mmol), 2-methylpropane-2-sulfinamide (173 mg, 1.42 mmol) and titanium ethoxide (0.391 mL, 1.90 mmol) were dissolved in 2-Me THF (5 mL) and heated to reflux overnight. The reaction was stopped and was left to cool down to r.t. EtOAc and water were added under stirring. The mixture was left to stand still for 2 h. The organic phase was collected by filtration, dried using a phase separator and concentrated in vacuo. The crude product was purified by flash chromatography using a gradient of 0-30% EtOAc in heptane to give the title compound (290 mg, 69% yield): 1H NMR (500 MHz, CDCl3) δ ppm 1.35 (s, 9H) 1.48-1.54 (m, 1H) 1.61 (dd, 1H) 1.67-1.77 (m, 2H) 1.81-1.90 (m, 2H) 2.10 (br. s., 2H) 2.95-3.05 (m, 2H) 3.95-4.02 (m, 4H) 7.25 (s, 1H) 7.60 (dd, 1H) 8.62 (br. s., 1H); MS (ES+) m/z 440.0 [M+H]+.

Workup

  1. temperatureheated
  2. temperatureto reflux overnight
  3. waitwas left
  4. waitThe mixture was left
  5. filtrationThe organic phase was collected by filtration
  6. customdried
  7. concentrationconcentrated in vacuo
  8. customThe crude product was purified by flash chromatography

Sources & evidence

ORD record
ord-984563ebaa2342b3a9c646d53d6ca74f
Source dataset
uspto-grants-2016_02
Patent number
US09248129B2

Reaction notes

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