Boron Trichloride → 11-Allyl-6-hydroxy-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-trien-8-one

HRID 272603Notes

Reaction equation

HRID 272603 reaction equation
[CH2:1]([N:4]1[CH2:15][CH:14]2[CH2:16][CH:6]([C:7](=[O:19])[C:8]3[C:9]([O:17]C)=[CH:10][CH:11]=[CH:12][C:13]=32)[CH2:5]1)[CH:2]=[CH2:3].B(Cl)(Cl)Cl.C([O-])(O)=O.[Na+]>ClCCl>[CH2:1]([N:4]1[CH2:15][CH:14]2[CH2:16][CH:6]([C:7](=[O:19])[C:8]3[C:9]([OH:17])=[CH:10][CH:11]=[CH:12][C:13]=32)[CH2:5]1)[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 25135Boron TrichlorideHCID 516892Sodium BicarbonateHCID 5983786311-Allyl-6-methoxy-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-trien-8-one

Product 1

HCID 5983782411-Allyl-6-hydroxy-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-trien-8-oneYield 44.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

11-Allyl-6-methoxy-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-trien-8-one (1.20 g, 4.66 mmol) in dichloromethane (25 mL) was cooled to −78° C. and treated with BCl3 (10.3 mL, 1M in dichloromethane). The mixture was allowed to stir to ambient temperature for 18 h. The mixture was treated with half saturated aqueous NaHCO3 solution (100 mL), the layers were separated and extracted with dichloromethane (3×40 mL). The organic layer was washed with H2O (50 mL) and saturated aqueous NaCl solution (50 mL), dried through a cotton plug and concentrated to an oil. Purification by chromatography on silica gel eluting with 15% EtOAc/hexanes afforded an oil (500 mg, 44%). (TLC 25% EtOAc/hexanes Rf 0.52); 1H NMR (400 MHz, CDCl3) δ 7.33 (dd, J=8.3, 7.5 Hz, 1H), 6.78 (dd, J=8.3, 1.0 Hz, 1H), 6.67 (dd, J=7.5, 1.0 Hz, 1H), 5.52 (m, 1H), 4.95 (m, 2H), 3.16 (br d, J=10.8 Hz, 1H), 3.05 (br s, 1H), 2.85 br, d, J=6.0 Hz, 2H), 2.78 (dd, J=9.5, 1.3 Hz, 1H), 2.65 (d, J=1.7 Hz, 1H), 2.41 (dd, J=10.8, 2.4 Hz, 1H), 2.33 (m, 2H), 1.86 (ddd, J=12.9, 5.9, 2.9 Hz, 1H); GCMS m/z 243 (M)+.

Workup

  1. customthe layers were separated
  2. extractionextracted with dichloromethane (3×40 mL)
  3. washThe organic layer was washed with H2O (50 mL) and saturated aqueous NaCl solution (50 mL)
  4. customdried through a cotton plug
  5. concentrationconcentrated to an oil
  6. customPurification by chromatography on silica gel eluting with 15% EtOAc/hexanes

Sources & evidence

ORD record
ord-8502745df7f246d383870129905d7f9e
Source dataset
uspto-grants-2008_11
Patent number
US07456177B2

Reaction notes

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