Toluene → (R)-2-Benzhydryloxirane

HRID 1897900Notes

Reaction equation

HRID 1897900 reaction equation
C1(C)C=CC=CC=1.[CH:8]([CH:21]1[CH2:23][O:22]1)([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1>CC(C1C=C(C=N[C@H]2[C@H](N=CC3C([O-])=C(C(C)(C)C)C=C(C(C)(C)C)C=3)CCCC2)C([O-])=C(C(C)(C)C)C=1)(C)C.[Co+2].C(O)(=O)C.O>[CH:8]([C@@H:21]1[CH2:23][O:22]1)([C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

6

Reactant 2

HCID 1140TolueneHCID 125490582-(Diphenylmethyl)oxirane

Product 1

HCID 11789056(R)-2-BenzhydryloxiraneYield 46.8%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidCatalystHCID 9873565cobaltous;2,4-ditert-butyl-6-[[(1R,2R)-2-[(3,5-ditert-butyl-2-oxido-phenyl)methyleneamino]cyclohexyl]iminomethyl]phenolateCatalystHCID 962WaterSolvent2×

Procedure

A mixture of (R,R)-(−)-N,N′-Bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane diaminocobalt (II) (0.22 g, 0.37 mmol, 0.8%), toluene (5 ml), and acetic acid (0.044 g, 0.74 mmol) was stirred for 1 h at room temperature. The solvent was removed in vacuo and the residue was dried. 2-Benzhydryl-oxirane (9.6 g, 45.7 mmol) was added in one portion and stirred, the mixture was then cooled by means of an ice-bath. H2O (0.58 g, 32 mmol) was slowly added over a 30-min period. After water addition, the ice bath was removed and the reaction mixture was stirred at room temperature for 72 h. Compounds were separated via flash chromatography on silica gel column to give (2R)-2-benzhydryl-oxirane (23a) 4.5 g ([α]D=(+)9.58, c=1, MeOH) and (2S)-3,3-diphenyl-propane-1,2-diol 24.3.53 g ([α]D=(+)48, c=1, MeOH, ee=97%). The proton and carbon NMR data of (2R)-2-benzhydryl-oxirane was identical to the racemate 2-benzhydryl-oxirane.

Workup

  1. customThe solvent was removed in vacuo
  2. customthe residue was dried
  3. stirringstirred
  4. temperaturethe mixture was then cooled by means of an ice-bath
  5. customthe ice bath was removed
  6. stirringthe reaction mixture was stirred at room temperature for 72 h
  7. customCompounds were separated via flash chromatography on silica gel column

Sources & evidence

ORD record
ord-268b7d1fcd8843968b99eb2d57b2efe1
Source dataset
uspto-grants-2013_08
Patent number
US08519159B2

Reaction notes

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