Acetic Acid → (R)-2-Benzhydryloxirane

HRID 606991ノート

反応式

HRID 606991 の反応式
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

参加物

7

反応物 3

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

生成物 2

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

試薬・触媒・溶媒 2

HCID 9873565cobaltous;2,4-ditert-butyl-6-[[(1R,2R)-2-[(3,5-ditert-butyl-2-oxido-phenyl)methyleneamino]cyclohexyl]iminomethyl]phenolate触媒HCID 962Water溶媒2 回

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-09295d6f76c343b49b3d8fca8af1209e
出典データセット
uspto-grants-2011_03
特許番号
US07915433B2

反応ノート

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