Nitrogen → tert-butyl (E)-3-(8-oxo-6,7,8,9-tetrahydro-5H-pyrido[2,3-b]azepin-3-yl)acrylate

HRID 1297422Notes

Reaction equation

HRID 1297422 reaction equation
Br[C:2]1[CH:13]=[N:12][C:5]2[NH:6][C:7](=[O:11])[CH2:8][CH2:9][CH2:10][C:4]=2[CH:3]=1.[C:14]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])(=[O:17])[CH:15]=[CH2:16].CCN(C(C)C)C(C)C.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.N#N>C(#N)CC.CC([O-])=O.CC([O-])=O.[Pd+2]>[O:11]=[C:7]1[NH:6][C:5]2[N:12]=[CH:13][C:2](/[CH:16]=[CH:15]/[C:14]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])=[CH:3][C:4]=2[CH2:10][CH2:9][CH2:8]1

Participants

8

Reactant 5

HCID 947NitrogenHCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 81531DiisopropylethylamineHCID 221390243-Bromo-5,6,7,9-tetrahydro-pyrido[2,3-b]azepin-8-one

Product 1

HCID 23574465tert-butyl (E)-3-(8-oxo-6,7,8,9-tetrahydro-5H-pyrido[2,3-b]azepin-3-yl)acrylateYield 58.5%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 7854PropionitrileSolvent

Procedure

A solution of 3-bromo-5,6,7,9-tetrahydro-pyrido[2,3-b]azepin-8-one (1.00 g, 4.15 mmole), tert-butyl acrylate (0.67 mL, 4.60 mmole), DIEA (1.45 mL, 8.30 mmole), Pd(OAc)2 (0.09 g, 0.42 mmole) and P(o-tol)3 (0.25 g, 0.85 mmole) in propionitrile (25 mL) was purged with N2 and then heated at reflux overnight. The dark mixture was filtered through a pad of celite®, and the filter pad was rinsed with acetonitrile (250 mL). The filtrate was concentrated in vacuo, and the residue was purified by flash chromatography on silica gel (ethyl acetate). The title compound (0.70 g, 58%) was obtained as a light yellow solid after drying in vacuo: MS (ES) m/e 289 (M+H)+.

Workup

  1. temperatureheated
  2. temperatureat reflux overnight
  3. filtrationThe dark mixture was filtered through a pad of celite®
  4. washthe filter pad was rinsed with acetonitrile (250 mL)
  5. concentrationThe filtrate was concentrated in vacuo
  6. customthe residue was purified by flash chromatography on silica gel (ethyl acetate)

Sources & evidence

ORD record
ord-a1bb717a612d41199f5f36e2bc1f5cdf
Source dataset
uspto-grants-2007_07
Patent number
US07250424B2

Reaction notes

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