Pyridine → (S)-2-tert-butoxy-2-(7-(4-chlorophenyl)-5-methyl-2-(3-(trifluoromethylsulfonyloxy)phenyl)benzo[d]thiazol-6-yl)ethyl pivalate

HRID 879279Notes

Reaction equation

HRID 879279 reaction equation
[C:1]([O:7][CH2:8][C@H:9]([C:15]1[C:37]([CH3:38])=[CH:36][C:18]2[N:19]=[C:20]([C:22]3[CH:27]=[CH:26][CH:25]=[C:24]([O:28]CC4C=CC=CC=4)[CH:23]=3)[S:21][C:17]=2[C:16]=1[C:39]1[CH:44]=[CH:43][C:42]([Cl:45])=[CH:41][CH:40]=1)[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[H][H].N1C=CC=CC=1.[O:54](S(C(F)(F)F)(=O)=O)[S:55]([C:58]([F:61])([F:60])[F:59])(=O)=[O:56]>CCO.CCOC(C)=O.[Pd]>[C:1]([O:7][CH2:8][C@@H:9]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[C:15]1[C:37]([CH3:38])=[CH:36][C:18]2[N:19]=[C:20]([C:22]3[CH:27]=[CH:26][CH:25]=[C:24]([O:28][S:55]([C:58]([F:61])([F:60])[F:59])(=[O:56])=[O:54])[CH:23]=3)[S:21][C:17]=2[C:16]=1[C:39]1[CH:40]=[CH:41][C:42]([Cl:45])=[CH:43][CH:44]=1)(=[O:6])[C:2]([CH3:4])([CH3:3])[CH3:5]

Participants

7

Reactant 4

HCID 1049PyridineHCID 67749Trifluoromethanesulfonic anhydrideHCID 86699795(S)-2-(2-(3-(benzyloxy)phenyl)-7-(4-chlorophenyl)-5-methylbenzo[d]thiazol-6-yl)-2-tert-butoxyethyl pivalateHCID 178418361HCID 178418361, compound

Product 1

HCID 86699797(S)-2-tert-butoxy-2-(7-(4-chlorophenyl)-5-methyl-2-(3-(trifluoromethylsulfonyloxy)phenyl)benzo[d]thiazol-6-yl)ethyl pivalateYield 82.5%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21584252Ethanol ethylacetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (S)-2-(2-(3-(benzyloxy)phenyl)-7-(4-chlorophenyl)-5-methylbenzo[d]thiazol-6-yl)-2-tert-butoxyethyl pivalate (410 mg, 0.638 mmol) in EtOH/EtOAc (1:1, 4 mL) was added Pd/C (10%, 600 mg). Then hydrogen balloon was attached to the flask, and the reaction was reacted at room temperature for 1 h. After the reaction was finished, the catalyst was removed over Celite pad and the solution was concentrated down to dryness. The residue was dissolved in DCM (5 mL), to the solution was added pyridine (2 mL), Tf2O (210 μL, 1.25 mmol) at 0° C. and the reaction was stirred at 0° C. for 1 h. Then the reaction was quenched by sat. NaHCO3, extracted by DCM, dried over MgSO4, filtered, concentrated down and purified by silica gel column (0-40% EtOAc in hexanes) to give the product (360 mg, 82%). LCMS-ESI+: calc'd for C32H33ClF3NO6S2: 684.1 (M+H+); Found: 684.1 (M+H+).

Workup

  1. customthe reaction was reacted at room temperature for 1 h
  2. customthe catalyst was removed over Celite pad
  3. concentrationthe solution was concentrated down to dryness
  4. dissolutionThe residue was dissolved in DCM (5 mL), to the solution
  5. customThen the reaction was quenched by sat. NaHCO3
  6. extractionextracted by DCM
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated down
  10. custompurified by silica gel column (0-40% EtOAc in hexanes)

Sources & evidence

ORD record
ord-6b793dbbe0734cc5a8838d4f871f7129
Source dataset
uspto-grants-2015_03
Patent number
US08987250B2

Reaction notes

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