Triethylamine → HCID 10905566, compound

HRID 430885Notes

Reaction equation

HRID 430885 reaction equation
FC(F)(F)S(O[C:7]1[CH:16]=[CH:15][C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:8]=1[C:17]1[C:26]2[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=2)[CH:20]=[CH:19][C:18]=1[O:27][CH2:28][C:29]1[CH:34]=[CH:33][C:32]([O:35][CH3:36])=[CH:31][CH:30]=1)(=O)=O.C(=[NH:52])(C1C=CC=CC=1)C1C=CC=CC=1.C(N(CC)CC)C.C(=O)([O-])[O-].[Cs+].[Cs+]>C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2OC2C=CC=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[NH2:52][C:7]1[CH:16]=[CH:15][C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:8]=1[C:17]1[C:26]2[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=2)[CH:20]=[CH:19][C:18]=1[O:27][CH2:28][C:29]1[CH:34]=[CH:33][C:32]([O:35][CH3:36])=[CH:31][CH:30]=1

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 10796Cesium carbonateHCID 136809Benzophenone imineHCID 110927382-(Trifluoromethanesulfonyloxy)-2'-(4'-methoxybenzyloxy)-1,1'-binaphthyl

Product 1

HCID 10905566HCID 10905566, compoundYield 91%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 4285986Bis[2-(diphenylphosphino)phenyl] etherCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A flask containing 2-(trifluoromethanesulfonyloxy)-2′-(4′-methoxybenzyloxy)-1,1′-binaphthyl (539 mg, 1.00 mmol), benzophenone imine (503 μL, 3.00 mmol), palladium acetate (11.2 mg, 0.0500 mmol), bis[2-(diphenylphosphino)phenyl]ether [DPE-phos] (40.4 mg, 0.0750 mmol), and triethylamine (70 μL) was purged with a gentle stream of argon for 20 minutes while stirring the mixture at room temperature. After this time, cesium carbonate (488 mg, 1.50 mmol) was added under a heavy stream of argon. The reaction mixture was then heated to 90° C. under an argon atmosphere for 32 hours. The reaction mixture was then cooled to room temperature and diluted with 30 mL of ethyl acetate. The organic solution was washed with a saturated aqueous sodium chloride solution (30 mL). The organic solution was dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was redissolved in 10 mL of tetrahydrofuran and 10 mL of ethanol to be treated with 2.0 mL of 2.0 M aqueous hydrochloric acid. The solution was stirred for 1 hour and then was diluted with 30 mL of aqueous 2.0 M sodium hydroxide. The organics were extracted with 40 mL of ethyl acetate. The organic layer was washed with 30 mL of a saturated aqueous sodium chloride solution. The organic solution was dried over anhydrous sodium sulfate and was concentrated in vacuo. The product was isolated as a white solid (369 mg, 91%) by crystallization from isopropanol.

Workup

  1. customwas purged with a gentle stream of argon for 20 minutes
  2. temperatureThe reaction mixture was then heated to 90° C. under an argon atmosphere for 32 hours
  3. temperatureThe reaction mixture was then cooled to room temperature
  4. washThe organic solution was washed with a saturated aqueous sodium chloride solution (30 mL)
  5. dry with materialThe organic solution was dried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo
  7. dissolutionThe residue was redissolved in 10 mL of tetrahydrofuran
  8. addition10 mL of ethanol to be treated with 2.0 mL of 2.0 M aqueous hydrochloric acid
  9. stirringThe solution was stirred for 1 hour
  10. additionwas diluted with 30 mL of aqueous 2.0 M sodium hydroxide
  11. extractionThe organics were extracted with 40 mL of ethyl acetate
  12. washThe organic layer was washed with 30 mL of a saturated aqueous sodium chloride solution
  13. dry with materialThe organic solution was dried over anhydrous sodium sulfate
  14. concentrationwas concentrated in vacuo

Sources & evidence

ORD record
ord-0f4a0a99397d4b16a9b353a9bea635c9
Source dataset
uspto-grants-2001_11
Patent number
US06323366B1

Reaction notes

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