1,8-Diazabicyclo(5.4.0)undec-7-ene → (S)-tert-Butyl 5-azido-7-methyl-8-trifluoromethyl-2,3,4,5-tetrahydrobenzo[b]azepine-1-carboxylate

HRID 507030Notes

Reaction equation

HRID 507030 reaction equation
O[C@@H:2]1[CH2:8][CH2:7][CH2:6][N:5]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[C:4]2[CH:16]=[C:17]([C:21]([F:24])([F:23])[F:22])[C:18]([CH3:20])=[CH:19][C:3]1=2.C1(P([N:39]=[N+:40]=[N-:41])(C2C=CC=CC=2)=O)C=CC=CC=1.C1CCN2C(=NCCC2)CC1>C1(C)C=CC=CC=1>[N:39]([C@H:2]1[CH2:8][CH2:7][CH2:6][N:5]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[C:4]2[CH:16]=[C:17]([C:21]([F:24])([F:23])[F:22])[C:18]([CH3:20])=[CH:19][C:3]1=2)=[N+:40]=[N-:41]

Participants

5

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 199401P,P-Diphenylphosphinic azideHCID 59432478(R)-tert-Butyl 5-hydroxy-7-methyl-8-(trifluoromethyl)-2,3,4,5-tetrahydro-1H-benzo[b]azepine-1-carboxylate

Product 1

HCID 59432320(S)-tert-Butyl 5-azido-7-methyl-8-trifluoromethyl-2,3,4,5-tetrahydrobenzo[b]azepine-1-carboxylateYield 85%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Heat a mixture of (R)-tert-butyl 5-hydroxy-7-methyl-8-trifluoromethyl-2,3,4,5-tetrahydrobenzo[b]azepine-1-carboxylate (1.60 g, 4.65 mmol), diphenylphosphoryl azide (DPPA, 1.4 mL, 6.50 mmol) and DBU (1.0 mL, 6.50 mmol) in toluene (20 mL) at 65° C. under nitrogen for 12 h. Add silica gel to the cooled mixture and remove the solvents under reduced pressure. Purify the residue by column chromatography, eluting with ethyl acetate/hexanes (1:2), to provide the title compound as a colorless oil (1.45 g, 85%). APCI MS m/z 356 (M−N2)−.

Workup

  1. temperatureHeat
  2. customAdd silica gel to the cooled mixture and remove the solvents under reduced pressure
  3. customPurify the residue by column chromatography
  4. washeluting with ethyl acetate/hexanes (1:2)

Sources & evidence

ORD record
ord-5cad877c0a614eea80780fe349c6d4e0
Source dataset
uspto-grants-2010_08
Patent number
US07786108B2

Reaction notes

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