(S)-tert-butyl 1-(benzyl(but-3-enyl)amino)-1-oxopent-4-en-2-ylcarbamate → (S,Z)-tert-butyl 1-benzyl-2-oxo-1,2,3,4,7,8-hexahydroazocin-3-ylcarbamate

HRID 529508Notes

Reaction equation

[CH2:1]([N:8]([CH2:23][CH2:24][CH:25]=C)[C:9](=[O:22])[C@@H:10]([NH:14][C:15](=[O:21])[O:16][C:17]([CH3:20])([CH3:19])[CH3:18])[CH2:11][CH:12]=C)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>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>[CH2:1]([N:8]1[CH2:23][CH2:24][CH:25]=[CH:12][CH2:11][C@H:10]([NH:14][C:15](=[O:21])[O:16][C:17]([CH3:19])([CH3:18])[CH3:20])[C:9]1=[O:22])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

Conditions

Temperature: 57.5 °C

Procedure

A solution of (S)-tert-butyl 1-(benzyl(but-3-enyl)amino)-1-oxopent-4-en-2-ylcarbamate (255 mg, 0.711 mmol) in ClCH2CH2Cl (120 mL) was degassed with argon for 5 min. Then, the Grubbs II catalyst (30 mg, 0.036 mmol) was added. The reaction mixture was stirred at 55-60° C. under argon for 13 hr. The reaction mixture was then cooled to rt and concentrated. 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 1-benzyl-2-oxo-1,2,3,4,7,8-hexahydroazocin-3-ylcarbamate (110 mg, 0.333 mmol, 46.8% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ ppm 7.36-7.19 (m, 5H), 5.95 (d, J=6.5 Hz, 1H), 5.75-5.65 (m, 1H), 5.49-5.39 (m, 1H), 4.96 (d, J=14.8 Hz, 1H), 4.88 (q, J=6.8 Hz, 1H), 4.17 (d, J=14.9 Hz, 1H), 3.89-3.75 (m, 1H), 3.17 (dt, J=15.3, 5.8 Hz, 1H), 2.94-2.83 (m, 1H), 2.51-2.39 (m, 1H), 2.38-2.25 (m, 2H), 1.46 (s, 9H).

Workup

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

Sources & evidence

ORD record: ord-30f37e035ce5401e8ecb1e9cf7f873fd
Source dataset: uspto-grants-2016_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09346852B2

Reaction notes

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