Ethyl Acetate → HCID 89968662, compound

HRID 1468704Notes

Reaction equation

HRID 1468704 reaction equation
Br[C:2]1[S:3][C:4]2[C:10]([O:11][S:12]([C:15]([F:18])([F:17])[F:16])(=[O:14])=[O:13])=[C:9]([C@H:19]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])[C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:8]([CH3:30])=[CH:7][C:5]=2[N:6]=1.[NH4+].[Cl-].[CH3:33][CH2:34][O:35][C:36](C)=[O:37]>CN(C=O)C.[Cu](I)I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:26]([O:25][C@@H:19]([C:9]1[C:8]([CH3:30])=[CH:7][C:5]2[N:6]=[C:2]([C:36]([O:35][CH2:34][CH3:33])=[O:37])[S:3][C:4]=2[C:10]=1[O:11][S:12]([C:15]([F:18])([F:17])[F:16])(=[O:14])=[O:13])[C:20]([O:22][CH2:23][CH3:24])=[O:21])([CH3:29])([CH3:28])[CH3:27]

Participants

7

Reactant 3

HCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 86699785(S)-ethyl 2-(2-bromo-5-methyl-7-(trifluoromethylsulfonyloxy)benzo[d]thiazol-6-yl)-2-tert-butoxyacetate

Product 1

HCID 89968662HCID 89968662, compound

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
45 °C

Procedure

To a a solution of (S)-ethyl 2-(2-bromo-5-methyl-7-(trifluoromethylsulfonyloxy)benzo[d]thiazol-6-yl)-2-tert-butoxyacetate (32) (1.07 g, 2.00 mmol) in DMF (10 mL) was added tributyl(1-ethoxyvinyl)starmane (867 mg, 2.40 mmol), copper iodide (38 mg, 0.20 mmol), and Pd(PPh3)4 (116 mg, 0.10 mmol). The reaction mixture was stirred at 45° C. for 2.5 h. A saturated solution of NH4Cl was added and EtOAc. The layers were separated, and the aqueous layer was extracted with EtOAc. The combined organic layers were dried, filtered, and concentrated in vacuo. Methanol and CH2Cl2 (1:1, 20 mL) added. The mixture was cooled to −78° C. and ozone (O3) was bubbled through the solution for about 15 min until the reaction mixture was blue-green. Dimethysulfide (1 mL) was added and the reaction was stirred at rt for 20 min. The mixture was concentrated in vacuo and purified by column chromatography (EtOAc/hexanes) to give 811 mg of 37.

Workup

  1. customThe layers were separated
  2. extractionthe aqueous layer was extracted with EtOAc
  3. customThe combined organic layers were dried
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. additionMethanol and CH2Cl2 (1:1, 20 mL) added
  7. temperatureThe mixture was cooled to −78° C.
  8. customozone (O3) was bubbled through the solution for about 15 min until the reaction mixture
  9. additionDimethysulfide (1 mL) was added
  10. stirringthe reaction was stirred at rt for 20 min
  11. concentrationThe mixture was concentrated in vacuo
  12. custompurified by column chromatography (EtOAc/hexanes)

Sources & evidence

ORD record
ord-695468eddf0e4150b5ad601ea79fdf77
Source dataset
uspto-grants-2015_04
Patent number
US09006229B2

Reaction notes

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