5-allyl-4-[2-(4-fluoro-phenyl)-allyl]-2,4,8-trimethyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole → 5-(4-Fluoro-phenyl)-2,3a,10-trimethyl-1,2,3,3a,4,7-hexahydro-2,7a-diaza-cyclohepta[jk]fluorene

HRID 576515Notes

Reaction equation

HRID 576515 reaction equation
[CH2:1]([N:4]1[C:12]2[CH:11]=[CH:10][C:9]([CH3:13])=[CH:8][C:7]=2[C:6]2[CH2:14][N:15]([CH3:29])[CH2:16][C:17]([CH2:19][C:20]([C:22]3[CH:27]=[CH:26][C:25]([F:28])=[CH:24][CH:23]=3)=[CH2:21])([CH3:18])[C:5]1=2)C=C>C(Cl)Cl.CC1C=C(C)C(N2C(=[Ru](Cl)(Cl)=CC3C=CC=CC=3OC(C)C)N(C3C(C)=CC(C)=CC=3C)CC2)=C(C)C=1>[F:28][C:25]1[CH:26]=[CH:27][C:22]([C:20]2[CH2:19][C:17]3([CH3:18])[CH2:16][N:15]([CH3:29])[CH2:14][C:6]4[C:7]5[CH:8]=[C:9]([CH3:13])[CH:10]=[CH:11][C:12]=5[N:4]([C:5]=43)[CH2:1][CH:21]=2)=[CH:23][CH:24]=1

Participants

4

Reactant 1

HCID 673567255-allyl-4-[2-(4-fluoro-phenyl)-allyl]-2,4,8-trimethyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole

Product 1

HCID 533547535-(4-Fluoro-phenyl)-2,3a,10-trimethyl-1,2,3,3a,4,7-hexahydro-2,7a-diaza-cyclohepta[jk]fluoreneYield 96.5%

Reagents, catalysts & solvents 2

HCID 11763533(1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene)(dichloro)((2-((propan-2-yl)oxy)phenyl)methylidene)rutheniumCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
80 °C

Procedure

5-Allyl-4-[2-(4-fluoro-phenyl)-allyl]-2,4,8-trimethyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole (100 mg, 0.25 mmol) was dissolved in DCM (15 mL) and purged with nitrogen. Hoveyda-Grubbs 2nd generation catalyst (10 mg, 0.015 mmol) was added and the reaction mixture was re-purged with nitrogen. The reaction mixture was heated at 80° C. for 6 h, cooled to RT, concentrated under reduced pressure and the residue purified by column chromatography using silica (100-200 mesh) eluting with 1% MeOH in DCM to obtain 87 mg of 5-(4-fluoro-phenyl)-2,3a,10-trimethyl-1,2,3,3a,4,7-hexahydro-2,7a-diaza-cyclohepta[jk]fluorene. 1H NMR (Oxalate salt, CD3OD) δ (ppm): 7.40 (m, 2H), 7.30 (d, 1H), 7.26 (s, 1H), 7.05 (m, 3H), 6.06 (d, 1H), 5.22 (m, 1H), 4.76 (m, 1H), 4.60-4.40 (m, 2H), 3.60 (m, 2H), 3.18 (s, 3H), 3.05 (m, 1H), 2.70 (m, 1H), 2.40 (s, 3H), 1.66 (s, 3H).

Workup

  1. custompurged with nitrogen
  2. customthe reaction mixture was re-purged with nitrogen
  3. temperaturecooled to RT
  4. concentrationconcentrated under reduced pressure
  5. customthe residue purified by column chromatography
  6. washeluting with 1% MeOH in DCM

Sources & evidence

ORD record
ord-cdb581e568cb43a1adf45b8e43d5b7d9
Source dataset
uspto-grants-2015_05
Patent number
US09040519B2

Reaction notes

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