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

HRID 639035
Notes
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Reaction equation

HRID 639035 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH:11]=[C:10](OS(C(F)(F)F)(=O)=O)[C:9]([O:20][CH2:21][C:22]2[CH:27]=[CH:26][C:25]([O:28][CH3:29])=[CH:24][CH:23]=2)=[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.[CH3:76][C:77]([S-:80])([CH3:79])[CH3:78].[Na+]>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]([S:80][C:77]([CH3:79])([CH3:78])[CH3:76])[C:9]([O:20][CH2:21][C:22]2[CH:23]=[CH:24][C:25]([O:28][CH3:29])=[CH:26][CH:27]=2)=[CH:8][N:7]=1)(=[O:3])[CH3:2]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 634876Binap, (A+-)-HCID 5147913Sodium 2-methyl-2-propanethiolateHCID 57423118(5-((4-Methoxybenzyl)oxy)-4-(((trifluoromethyl)sulfonyl)oxy)pyridin-2-yl)methyl acetate

Product 1

HCID 68576335[4-[(1,1-Dimethylethyl)thio]-5-({[4-(methoxy)phenyl]methyl}oxy)-2-pyridinyl]methyl acetateYield 100%

Reagents, catalysts & solvents 2

HCID 167845
palladium(II) acetate
Catalyst
HCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of (5-({[4-(methoxy)phenyl]methyl}oxy)-4-{[(trifluoromethyl)sulfonyl]oxy}-2-pyridinyl)methyl acetate (10 g, 23 mmol) in anhydrous toluene, (R)-(+)-2,2 bis(diphenylphosphino)-1,1-binaphthyl (312 mg, 0.4 mmol) was added. The reaction mixture was degassed before adding palladium acetate (103 mg, 0.4 mmol). Sodium 2-methyl-2-propanethiolate was added, the system degassed again and the reaction mixture was stirred at 60° C. for 3 hours, under argon atmosphere then at 70 oC for a further 18 hours. The reaction mixture was filtered and the filtrate was evaporated under vacuum. The residue was partitioned between ethyl acetate and water. The aqueous layer was extracted several times with ethyl acetate. The combined organic extracts were dried over magnesium sulfate and evaporated under vacuum. The residue was chromatographed on silica gel eluting with 20-35% ethyl acetate in hexane to afford the product as an oil (9.1 g, 100%); MS (+ve ion electrospray) m/z 376 (MH+).

Workup

  1. customThe reaction mixture was degassed
  2. customthe system degassed again
  3. waitat 70 oC for a further 18 hours
  4. filtrationThe reaction mixture was filtered
  5. customthe filtrate was evaporated under vacuum
  6. customThe residue was partitioned between ethyl acetate and water
  7. extractionThe aqueous layer was extracted several times with ethyl acetate
  8. dry with materialThe combined organic extracts were dried over magnesium sulfate
  9. customevaporated under vacuum
  10. customThe residue was chromatographed on silica gel eluting with 20-35% ethyl acetate in hexane

Sources & evidence

ORD record
ord-a46d095dcd18455cb68d07deacaa12cc
Source dataset
uspto-grants-2010_04
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07691850B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes