Binap, (A+-)- → (5-[(1,1-Dimethylethyl)thio]-4-[(phenylmethyl)oxy]-2-pyridinyl}methyl acetate

HRID 15159Notes

Reaction equation

HRID 15159 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH:11]=[C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:9](OS(C(F)(F)F)(=O)=O)=[CH:8][N:7]=1)(=[O:3])[CH3:2].C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Na].[CH3:75][C:76]([SH:79])([CH3:78])[CH3:77]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:1]([O:4][CH2:5][C:6]1[CH:11]=[C:10]([O:12][CH2:13][C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[C:9]([S:79][C:76]([CH3:78])([CH3:77])[CH3:75])=[CH:8][N:7]=1)(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 634876Binap, (A+-)-HCID 450519182-Propanethiol, 2-methyl-, sodium saltHCID 87432463(4-[(Phenylmethyl)oxy]-5-{[(trifluoromethyl)sulfonyl]oxy}-2-pyridinyl)methyl acetate

Product 1

HCID 68598711(5-[(1,1-Dimethylethyl)thio]-4-[(phenylmethyl)oxy]-2-pyridinyl}methyl acetate

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of (4-[(phenylmethyl)oxy]-5-{[(trifluoromethyl)sulfonyl]oxy}-2-pyridinyl)methyl acetate (12.15 g, 30 mmol) in toluene (500 ml) was added (R)-(+)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (1.87 g, 3 mmol). The reaction mixture was purged with argon. Palladium acetate (663 mg, 3 mmol) was added and the mixture was stirred for 10 minutes. 2-Methyl-2-propanethiol sodium salt (4.69, 41.8 mmol) was added and the reaction mixture was flushed again with argon then heated to 80° C. for 7 hours then cooled. The solvent was evaporated. The residue was partitioned between a 1:1 mixture of water and EtOAc. The organic layer was separated and washed with brine, dried over magnesium sulphate and filtered through Kieselguhr. The residue was chromatographed eluting with s 4:1 mixture of hexane:EtOAc affording the product (8.3 g, 80%).

Workup

  1. customThe reaction mixture was purged with argon
  2. customthe reaction mixture was flushed again with argon
  3. temperaturethen cooled
  4. customThe solvent was evaporated
  5. customThe residue was partitioned between a 1:1 mixture of water and EtOAc
  6. customThe organic layer was separated
  7. washwashed with brine
  8. dry with materialdried over magnesium sulphate
  9. filtrationfiltered through Kieselguhr
  10. customThe residue was chromatographed
  11. washeluting with s 4:1 mixture of hexane

Sources & evidence

ORD record
ord-edb8414ff76a4ea0a3c5adfa3c00c2f2
Source dataset
uspto-grants-2010_06
Patent number
US07732460B2

Reaction notes

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