Nitromethane → Cis-2-methyl-1,2,3,3a,4,5,6,10b-octahydrobenzo[3,4]cyclohepta[1,2-c]pyrrole

HRID 716014Notes

Reaction equation

HRID 716014 reaction equation
[CH:1]([NH:4][CH:5]([CH3:7])C)([CH3:3])C.[CH2:8]([Li])CCC.[N+](C)([O-])=O.[CH:17]1[C:22]2C=C[CH2:25][CH2:26][CH2:27][C:21]=2[CH:20]=[CH:19][CH:18]=1>O1CCCC1.O>[CH3:8][N:4]1[CH2:1][C@H:3]2[C:20]3[CH:19]=[CH:18][CH:17]=[CH:22][C:21]=3[CH2:27][CH2:26][CH2:25][C@H:7]2[CH2:5]1

Participants

7

Reactant 4

HCID 6375NitromethaneHCID 7912DiisopropylamineHCID 5822646,7-Dihydro-5H-benzocyclohepteneHCID 178418339Butyllithium

Product 1

HCID 66821233Cis-2-methyl-1,2,3,3a,4,5,6,10b-octahydrobenzo[3,4]cyclohepta[1,2-c]pyrrole

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To diisopropylamine (808 mg, 8.0 mmol) in tetrahydrofuran (3 mL) was added n-butyllithium (4.0 mL, 2.0 N in hexanes, 8.0 mmol) at −78° C. followed by the addition of nitromethane (300 mg, 4.0 mmol). The mixture was stirred for 10 min and (Z)-6,7-dihydro-5H-benzo[7]annulene (288 mg, 2.0 mmol) in tetrahydrofuran (1 mL) was added. The mixture was warmed to room temperature for 10 minutes and stirred at room temperature for 4 hours. Water was added and the mixture was extracted with ethyl acetate. The crude material was purified by silica gel column chromatography eluting with ethyl acetate to afford the title compound. 1H NMR (500 MHz, DMSO-d6) δ ppm 7.14 (m, 2H), 7.07 (m, 2H), 3.55 (dd, J=17.4, 10.0 Hz, 1H), 3.21 (t, J=8.1 Hz, 1H), 2.97 (t, J=8.3 Hz, 1H), 2.75 (td, J=12.7, 6.9 Hz, 1H), 2.56 (m, 1H), 2.38 (dt, J=11.1, 5.6 Hz, 1H), 2.36 (m, 1H), 2.26 (s, 3H), 1.66 (m, 2H), 1.44 (m, 1H), 1.33 (dd, J=13.7, 6.4 Hz, 1H), and 0.87 (m, 1H); MS (ESI+) m/z 202 [M+H]+.

Workup

  1. stirringstirred at room temperature for 4 hours
  2. extractionthe mixture was extracted with ethyl acetate
  3. customThe crude material was purified by silica gel column chromatography
  4. washeluting with ethyl acetate

Sources & evidence

ORD record
ord-2b7c87e6744e4839afea0daf5a840eb5
Source dataset
uspto-grants-2015_11
Patent number
US09187483B2

Reaction notes

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