tert-Butyl acrylate → HCID 57742070, compound

HRID 1880001Notes

Reaction equation

HRID 1880001 reaction equation
Br[C:2]1[CH:12]=[N:11][C:10]2[NH:9][C:8](=[O:13])[C:7]([CH3:15])([CH3:14])[CH2:6][O:5][C:4]=2[CH:3]=1.[C:16]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])(=[O:19])[CH:17]=[CH2:18].CCN(C(C)C)C(C)C.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:14][C:7]1([CH3:15])[CH2:6][O:5][C:4]2[CH:3]=[C:2](/[CH:18]=[CH:17]/[C:16]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH:12]=[N:11][C:10]=2[NH:9][C:8]1=[O:13]

Participants

7

Reactant 4

HCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 81531DiisopropylethylamineHCID 593328468-bromo-3,3-dimethyl-2,3-dihydropyrido[3,2-b][1,4]oxazepin-4(5H)-one

Product 1

HCID 57742070HCID 57742070, compoundYield 87.3%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Procedure

A solution of 8-bromo-3,3-dimethyl-2,3-dihydropyrido[3,2-b][1,4]oxazepin-4(5H)-one (1 g, 3.6 mmol), t-butyl acrylate (1.38 g, 10.8 mmol) and DIPEA (1.86 mL, 10.1 mmol) in DMF (10 mL) was purged with Ar for 10 min. Pd(OAc)2 (81 mg, 0.36 mmol) and P(o-tol)3 (218 mg, 0.72 mmol) were added and the mixture purged again then refluxed overnight. The crude mixture was evaporated in vacuo and chromatographed over silica eluting with methanol/dichloromethane to afford the title compound (1.0 g, 87%). 1H NMR (300 MHz, DMSO-d6) δ 10.13 (s, 1H), 8.26 (s, 1H), 7.77 (s, 1H), 7.47 (d, J=16.1 Hz, 1H), 6.53 (d, J=16.1 Hz, 1H), 4.05 (s, 2H), 1.53 (s, 9H), 1.47 (s, 6H)

Workup

  1. customthe mixture purged again
  2. temperaturethen refluxed overnight
  3. customThe crude mixture was evaporated in vacuo
  4. customchromatographed over silica eluting with methanol/dichloromethane

Sources & evidence

ORD record
ord-b2028232e8784ce393d45fb0f8892cd9
Source dataset
uspto-grants-2012_11
Patent number
US08318720B2

Reaction notes

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