tert-Butyl hydroperoxide → N-Benzyloxycarbonyl-4-[(R*)-2-methyl-sulfinylphenyl]piperidine

HRID 1082245Notes

Reaction equation

HRID 1082245 reaction equation
C(OC(N1CC[CH:14]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=2[S@@:23](C)=[O:24])CC1)=O)C1C=CC=CC=1.C([C@](C([O-])=O)(O)[C@](CC)(O)C([O-])=O)C.[CH2:40]([O:47][C:48]([N:50]1[CH2:55][CH2:54][CH:53](C2C=CC=CC=2SC)[CH2:52][CH2:51]1)=[O:49])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1.C(OO)(C)(C)C>ClCCl.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4].O>[CH2:40]([O:47][C:48]([N:50]1[CH2:55][CH2:54][CH:53]([C:22]2[C@@H:17]([CH3:14])[C:18](=[S:23]=[O:24])[CH:19]=[CH:20][CH:21]=2)[CH2:52][CH2:51]1)=[O:49])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1

Participants

8

Reactant 4

HCID 6410tert-Butyl hydroperoxideHCID 111106201-Benzyloxycarbonyl-4(2-methylthiophenyl)piperidineHCID 29414049diethyl-D-tartarateHCID 53634760N-Benzyloxycarbonyl-4-[(R*)-2-methylsulfinylphenyl]-piperidine

Product 1

HCID 86750107N-Benzyloxycarbonyl-4-[(R*)-2-methyl-sulfinylphenyl]piperidine

Reagents, catalysts & solvents 3

HCID 11026Titanium isopropoxideCatalystHCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent

Conditions

Temperature
-15 °C

Procedure

N-Benzyloxycarbonyl-4-[(R*)-2-methylsulfinylphenyl]-piperidine. To a solution of diethyl-D-tartarate (3.4 mL) in dichloromethane (50 mL) was added titanium tetraisopropoxide (3.0 mL) followed by water (0.18 mL). The resulting solution was stirred vigorously for 30 minutes, treated with N-benzyloxycarbony-4-(2-methylthiophenyl)piperidine (3.41 g), and cooled to -15° C. The reaction mixture was treated with tert-butylhydroperoxide (2 mL) drop wise over a period of 1 minute, and stirred at -15° C. for 40 hours. Water (4 mL) was added, and the solution was stirred vigorously for 1 hour and filtered through a bed of diatomous earth. The filtrate was stirred with 5% aqueous sodium hydroxide (100 mL) for 1 hour and was washed with brine (50 mL). The aqueous layer was extracted with dichloromethane and the combined organic layers were washed (brine), dried (anhydrous sodium sulfate), and evaporated to give a solid product which was crystallized from diisopropyl ether to afford N-Benzyloxycarbonyl-4-[(R*)-2-methyl-sulfinylphenyl]piperidine (3.0 g).

Workup

  1. stirringstirred at -15° C. for 40 hours
  2. stirringthe solution was stirred vigorously for 1 hour
  3. filtrationfiltered through a bed of diatomous earth
  4. stirringThe filtrate was stirred with 5% aqueous sodium hydroxide (100 mL) for 1 hour
  5. washwas washed with brine (50 mL)
  6. extractionThe aqueous layer was extracted with dichloromethane
  7. washthe combined organic layers were washed (brine)
  8. dry with materialdried (anhydrous sodium sulfate)
  9. customevaporated
  10. customto give a solid product which
  11. customwas crystallized from diisopropyl ether

Sources & evidence

ORD record
ord-09f6bee192ce4085a38ebf66bdb5f85c
Source dataset
uspto-grants-1996_12
Patent number
US05589489

Reaction notes

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