Acetic Acid → (R)-2-Benzhydryloxirane

HRID 78916Notes

Reaction equation

HRID 78916 reaction equation
C1(C)C=CC=CC=1.C(O)(=[O:10])C.[CH:12]([CH:25]1[CH2:27][O:26]1)([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=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].O>[CH:12]([C@@H:25]1[CH2:27][O:26]1)([C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[C:19]1([CH:12]([C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)[C@H:25]([OH:10])[CH2:27][OH:26])[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

Participants

7

Reactant 3

HCID 176Acetic AcidHCID 1140TolueneHCID 125490582-(Diphenylmethyl)oxirane

Product 2

HCID 11789056(R)-2-BenzhydryloxiraneHCID 54762284(2S)-3,3-diphenyl-propane-1,2-diol

Reagents, catalysts & solvents 2

HCID 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-3da5d0370acc4214b9452e07e6db9efd
Source dataset
uspto-grants-2014_09
Patent number
US08841464B2

Reaction notes

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