HCID 59574875, compound → HCID 49806337, compound

HRID 2381218Notes

Reaction equation

HRID 2381218 reaction equation
[CH2:1]([C:4]1([CH2:29][CH:30]=[CH2:31])[N:13]2[CH2:14][CH2:15][C:16]3[C:21]([CH:12]2[CH2:11][C:10]2[CH:9]=[CH:8][C:7]([O:25][CH3:26])=[C:6]([O:27][CH3:28])[C:5]1=2)=[CH:20][C:19]1[O:22][CH2:23][O:24][C:18]=1[CH:17]=3)C=C>ClCCl.Cl[Ru](=CC1C=CC=CC=1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)Cl>[CH3:28][O:27][C:6]1[C:5]2[C:4]3([CH2:1][CH:31]=[CH:30][CH2:29]3)[N:13]3[CH2:14][CH2:15][C:16]4[C:21]([CH:12]3[CH2:11][C:10]=2[CH:9]=[CH:8][C:7]=1[O:25][CH3:26])=[CH:20][C:19]1[O:22][CH2:23][O:24][C:18]=1[CH:17]=4

Participants

4

Reactant 1

HCID 59574875HCID 59574875, compound

Product 1

HCID 49806337HCID 49806337, compoundYield 4%

Reagents, catalysts & solvents 2

HCID 178479819HCID 178479819, compoundCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
58 °C

Procedure

To a solution of 8,8-diallyl-9,10-dimethoxy-5,8,13,13a-tetrahydro-6H-[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinoline (68 mg, 0.16 mmol) in dry dichloromethane (50 mL) was added Grubbs' catalyst I (32 mg, 0.04 mmol) under nitrogen. The mixture was heated to reflux for 72 h at 58° C. The reaction mixture was cooled and concentrated in vacuo. Purification by Waters Automated Flash System (column: Xterra 30 mm×100 mm, sample manager 2767, pump 2525, detector: ZQ mass and UV 2487, solvent system: acetonitrile and 0.1% ammonium hydroxide in water) afforded 9′,10′-dimethoxy-5′,6′,13′,13a′-tetrahydrospiro[cyclopent-3-ene-1,8′-[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinoline] (2.5 mg, 4%). LC/MS m/e calcd for C24H25NO4 (M+H)+: 392.47, observed: 392.3; 1H NMR (400 MHz, MeOD) δ ppm 2.34-2.43 (m, 2 H) 2.55-2.68 (m, 1 H) 2.68-2.75 (m, 1 H) 2.75-2.81 (m, 1 H) 2.85-2.92 (m, 1 H) 2.92-2.99 (m, 1 H) 3.03-3.10 (m, 1 H) 3.11 (d, J=3.03 Hz, 1 H) 3.14-3.18 (m, 1 H) 3.79 (s, 3 H) 3.84 (s, 3 H) 3.93-4.00 (m, 1 H) 5.78-5.83 (m, 1 H) 5.83-5.88 (m, 1 H) 5.90 (s, 2 H) 6.58 (s, 1 H) 6.78 (s, 1 H) 6.83 (m, 1 H) 6.91 (m, 1 H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureThe reaction mixture was cooled
  3. concentrationconcentrated in vacuo
  4. customPurification by Waters Automated Flash System (column: Xterra 30 mm×100 mm, sample manager 2767, pump 2525, detector: ZQ mass and UV 2487, solvent system: acetonitrile and 0.1% ammonium hydroxide in water)

Sources & evidence

ORD record
ord-8879d598cf4944dbaf54c79586c5e19f
Source dataset
uspto-grants-2012_09
Patent number
US08258149B2

Reaction notes

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