Acetic Acid → cis-N-phenyl-N'-(t-butyloxycarbonyl)-cyclohexane-1,2-diamine

HRID 7189Notes

Reaction equation

HRID 7189 reaction equation
[C:1]([O:5][C:6]([NH:8][CH:9]1[CH2:14][CH2:13][CH2:12][CH2:11][C:10]1=O)=[O:7])([CH3:4])([CH3:3])[CH3:2].[NH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.C(O)(=O)C.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>C1COCC1.C(Cl)Cl>[C:17]1([NH:16][C@@H:10]2[CH2:11][CH2:12][CH2:13][CH2:14][C@@H:9]2[NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 6115AnilineHCID 5049666Sodium triacetoxyborohydrideHCID 5075026tert-butyl N-(2-oxocyclohexyl)carbamate

Product 1

HCID 86587219cis-N-phenyl-N'-(t-butyloxycarbonyl)-cyclohexane-1,2-diamineYield 9%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2-[N-(t-butyloxycarbonyl)]amino-cyclohexanone (0.785 g, 3.69 mmol, aniline (0.68 mL, 7.46 mmol) and glacial acetic acid (0.22 mL) in THF (10 mL) was added NaBH(OAc)3 (1.173 g, 5.53 mmol) and the mixture was stirred at 60□ C. overnight. The reaction was cooled to room temperature, diluted with CH2Cl2 (60 mL) and washed with saturated aqueous NaHCO3 (50 mL). The aqueous phase was washed with CH2Cl2 (2×25 mL) and the combined organic extracts dried (Na2SO4), filtered and concentrated under reduced pressure. Purification and separation of the resultant brown oil by flash chromatography on silica gel (Hexanes/EtOAc, 9:1) afforded the low polarity cis-N-phenyl-N′-(t-butyloxycarbonyl)-cyclohexane-1,2-diamine isomer (0.095 g, 9%) and the high polarity trans-N-phenyl-N′-(t-butyloxycarbonyl)-cyclohexane-1,2-diamine isomer (0.412 g, 39%), both as pale yellow solids.

Workup

  1. customovernight
  2. washwashed with saturated aqueous NaHCO3 (50 mL)
  3. washThe aqueous phase was washed with CH2Cl2 (2×25 mL)
  4. dry with materialthe combined organic extracts dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customPurification and separation of the resultant brown oil by flash chromatography on silica gel (Hexanes/EtOAc, 9:1)

Sources & evidence

ORD record
ord-7b02c5e32cf643398422b61880a7076a
Source dataset
uspto-grants-2006_08
Patent number
US07084155B2

Reaction notes

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