tert-butyl (1S)-1-[(4-benzyl-2-vinyl-1-piperazinyl)carbonyl]-3-butenylcarbamate → tert-butyl (7S)-2-benzyl-6-oxo-1,2,3,4,6,7,8,10a-octahydropyrazino[1,2-a]azepin-7-ylcarbamate

HRID 1060616Notes

Reaction equation

HRID 1060616 reaction equation
[CH2:1]([N:8]1[CH2:13][CH2:12][N:11]([C:14]([C@@H:16]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:17][CH:18]=C)=[O:15])[CH:10]([CH:28]=C)[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>Cl[Ru](=CC1C=CC=CC=1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)Cl.C1(C)C=CC=CC=1>[CH2:1]([N:8]1[CH2:13][CH2:12][N:11]2[C:14](=[O:15])[C@@H:16]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:24])([CH3:26])[CH3:25])[CH2:17][CH:18]=[CH:28][CH:10]2[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 1

HCID 10200953tert-butyl (1S)-1-[(4-benzyl-2-vinyl-1-piperazinyl)carbonyl]-3-butenylcarbamate

Product 1

HCID 86585166tert-butyl (7S)-2-benzyl-6-oxo-1,2,3,4,6,7,8,10a-octahydropyrazino[1,2-a]azepin-7-ylcarbamateYield 44%

Reagents, catalysts & solvents 2

HCID 178479819HCID 178479819, compoundCatalystHCID 1140TolueneSolvent

Procedure

tert-Butyl (1S)-1-[(4-benzyl-2-vinyl-1-piperazinyl)carbonyl]-3-butenylcarbamate (250 mg, 0.63 mmol) and Grubb's catalyst (26 mg, 0.03 mmol) were combined in toluene (32 mL) at room temperature. This mixture was degassed via vacuum-argon three times at room temperature. Then CH2Cl2 (32 mL) was added in one portion. The reaction mixture was heated at reflux for 5 days, then concentrated in vacuo. The residue was purified by SGC (4:1 hex-EtOAc) to give the title product (103 mg, 44%) as a yellow powder. The 1H NMR spectrum was consistent with the presence of one diastereomer, not assigned. (300 MHz, CDCl3) δ 7.35-7.27 (m, 5H), 5.76-5.72 (m, 2H), 5.67-5.58 (m, 1H), 5.35-5.01 (m, 1H), 4.68 (br s, 1H), 4.00 (m, 1H), 3.64 (d, 1H, J=13.1 Hz), 3.42 (d, 1H, J=13.2 Hz), 3.09 (dt, 1H, J=13.5, 4.1 Hz), 2.91-2.86 (m, 1H), 2.76-2.72 (m, 2H), 2.26-2.00 (m, 3H), 1.44 (s, 9H) ppm.

Workup

  1. customThis mixture was degassed via vacuum-argon three times at room temperature
  2. additionThen CH2Cl2 (32 mL) was added in one portion
  3. temperatureThe reaction mixture was heated
  4. temperatureat reflux for 5 days
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by SGC (4:1 hex-EtOAc)

Sources & evidence

ORD record
ord-5e24598f3adc49c1a62328b9a4a58296
Source dataset
uspto-grants-2003_02
Patent number
US06525044B2

Reaction notes

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