Tert-butyl 1-(allyl(phenyl)amino)-3,3-dimethyl-1-oxopent-4-en-2-ylcarbamate → (Z)-tert-butyl 4,4-dimethyl-2-oxo-1-phenyl-2,3,4,7-tetrahydro-1H-azepin-3-ylcarbamate

HRID 529476Notes

Reaction equation

HRID 529476 reaction equation
[CH2:1]([N:4]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[C:5](=[O:20])[CH:6]([NH:12][C:13](=[O:19])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16])[C:7](C)([CH3:10])[CH:8]=C)[CH:2]=[CH2:3]>Cl[Ru](=C1N(C2C(C)=CC(C)=CC=2C)CCN1C1C(C)=CC(C)=CC=1C)(Cl)(=CC1C=CC=CC=1)[P](C1CCCCC1)(C1CCCCC1)C1CCCCC1.ClCCCl>[CH3:8][C:7]1([CH3:10])[CH:6]([NH:12][C:13](=[O:19])[O:14][C:15]([CH3:18])([CH3:16])[CH3:17])[C:5](=[O:20])[N:4]([C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[CH2:1][CH:2]=[CH:3]1

Participants

4

Reactant 1

HCID 68292774Tert-butyl 1-(allyl(phenyl)amino)-3,3-dimethyl-1-oxopent-4-en-2-ylcarbamate

Product 1

HCID 68292253(Z)-tert-butyl 4,4-dimethyl-2-oxo-1-phenyl-2,3,4,7-tetrahydro-1H-azepin-3-ylcarbamateYield 27%

Reagents, catalysts & solvents 2

HCID 178425456HCID 178425456, compoundCatalystHCID 111,2-DichloroethaneSolvent

Conditions

Temperature
60 °C

Procedure

To a round bottom flask was added tert-butyl 1-(allyl(phenyl)amino)-3,3-dimethyl-1-oxopent-4-en-2-ylcarbamate (60 mg, 0.17 mmol) and 1,2-dichloroethane (2 mL). The reaction was charged with argon and brought to 60° C. Then, the Grubbs II catalyst (21 mg, 0.025 mmol) was added and the reaction was stirred at 60° C. for 4 hr and then at rt overnight. The reaction was concentrated and the residue was purified by RP prep-HPLC (Method A) to give (Z)-tert-butyl 4,4-dimethyl-2-oxo-1-phenyl-2,3,4,7-tetrahydro-1H-azepin-3-ylcarbamate (15 mg, 0.045 mmol, 27% yield) as a clear oil. Anal. Calcd. for C19H26N2O3 m/z 330.2. found: 331.2 (M+H)+; 1H NMR (500 MHz, CDCl3) δ ppm 7.38 (t, J=7.69 Hz, 2H), 7.30-7.25 (m, 1H), 7.21 (d, J=7.03 Hz, 2H), 5.82-5.71 (m, 2H), 5.71-5.64 (m, 1H), 5.10 (d, J=8.35 Hz, 1H), 4.82 (d, J=17.58 Hz, 1H), 3.76 (dd, J=17.58, 7.91 Hz, 1H), 1.50-1.44 (m, 9H), 1.20-1.16 (m, 3H), 0.99 (s, 3H).

Workup

  1. additionThe reaction was charged with argon
  2. custombrought to 60° C
  3. customat rt
  4. customovernight
  5. concentrationThe reaction was concentrated
  6. customthe residue was purified by RP prep-HPLC (Method A)

Sources & evidence

ORD record
ord-1fc13f7a3e3d4eb88044fb87cc796efb
Source dataset
uspto-grants-2016_05
Patent number
US09346852B2

Reaction notes

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