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

HRID 529520Notes

Reaction equation

[CH2:1]([N:4]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:5](=[O:18])[C@@H:6]([NH:10][C:11](=[O:17])[O:12][C:13]([CH3:16])([CH3:15])[CH3:14])[CH2:7]C=C)[CH:2]=[CH2:3]>C(Cl)CCl.Cl[Ru](=C1N(C2C(C)=CC(C)=CC=2C)CCN1C1C(C)=CC(C)=CC=1C)(Cl)(=CC1C=CC=CC=1)[P](C1CCCCC1)(C1CCCCC1)C1CCCCC1>[O:18]=[C:5]1[C@@H:6]([NH:10][C:11](=[O:17])[O:12][C:13]([CH3:14])([CH3:16])[CH3:15])[CH2:7][CH:3]=[CH:2][CH2:1][N:4]1[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

Participants

Conditions

Temperature: 60 °C

Procedure

A solution of (S)-tert-butyl 1-(allyl(phenyl)amino)-1-oxopent-4-en-2-ylcarbamate (0.98 g, 2.97 mmol) in ClCH2CH2Cl (400 mL) was degassed with argon for 5 min. Then, Grubbs II catalyst (0.126 g, 0.148 mmol) was added. The reaction was stirred at 60° C. under argon for 16 hr. The reaction mixture was cooled to rt and concentrated to dryness. The brownish residue was purified using silica gel chromatography (ISCO system) eluting with a gradient of 0-30% EtOAc/Hex to give (S,Z)-tert-butyl 2-oxo-1-phenyl-2,3,4,7-tetrahydro-1H-azepin-3-ylcarbamate (0.787 g, 2.60 mmol, 88% yield) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.42-7.34 (m, 2H), 7.30-7.24 (m, 1H), 7.24-7.19 (m, 2H), 6.06-5.66 (m, 2H), 5.23-5.10 (m, 1H), 4.79 (dd, J=21.1, 17.3 Hz, 1H), 3.85-3.71 (m, 1H), 2.85-2.70 (m, 1H), 2.43-2.29 (m, 1H), 1.55-1.43 (m, 10H).

Workup

temperatureThe reaction mixture was cooled to rt
concentrationconcentrated to dryness
customThe brownish residue was purified
washeluting with a gradient of 0-30% EtOAc/Hex

Sources & evidence

ORD record: ord-702f572549d54c63959879fef0a20c27
Source dataset: uspto-grants-2016_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09346852B2

Reaction notes

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