Methyl Acrylate → (E)-3-{1'-tert-butoxycarbonyl-4-oxo-spiro[chromane-2,4'-piperidine]-6-yl}-acrylic acid methyl ester

HRID 518147

反応式

HRID 518147 の反応式
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11]2([CH2:22][C:21](=[O:23])[C:20]3[C:15](=[CH:16][CH:17]=[C:18](Br)[CH:19]=3)[O:14]2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[C:44]([O:48][CH3:49])(=[O:47])[CH:45]=[CH2:46]>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:49][O:48][C:44](=[O:47])/[CH:45]=[CH:46]/[C:18]1[CH:19]=[C:20]2[C:15](=[CH:16][CH:17]=1)[O:14][C:11]1([CH2:12][CH2:13][N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[CH2:9][CH2:10]1)[CH2:22][C:21]2=[O:23]

参加物

6

反応物 3

HCID 7294Methyl AcrylateHCID 11776TriphenylphosphineHCID 2794759tert-Butyl 6-bromo-4-oxospiro[chroman-2,4'-piperidine]-1'-carboxylate

生成物 1

HCID 52952087(E)-3-{1'-tert-butoxycarbonyl-4-oxo-spiro[chromane-2,4'-piperidine]-6-yl}-acrylic acid methyl ester収率 56.5%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
100 °C

実験手順

A mixture of 6-bromo-4-oxo-spiro[chromane-2,4′-piperidine]-1′-carboxylic acid tert-butyl ester (1.04 g, 2.62 mmol), Pd(OAc)2 (59 mg, 0.262 mmol), PPh3 (137 mg, 0.52 mmol), TEA (0.73 ml, 5.2 mmol), methyl acrylate (0.47 ml, 5.2 mmol) in dry DMF (10 ml) was heated at 100° C. for 8 h. The mixture was cooled down to RT, filtered on a celite pad and washed with AcOEt (100 ml). The filtrate was washed with NH4Cl and saturated NaHCO3 solution and brine. The organic phase was dried over Na2SO4 and evaporated under vacuum. The crude residue was purified by column chromatography (eluent: hexane/AcOEt 90:10 to 70:30) to give (E)-3-{1′-tert-butoxycarbonyl-4-oxo-spiro[chromane-2,4′-piperidine]-6-yl}-acrylic acid methyl ester (594 mg) as a light yellow solid.

後処理

  1. temperatureThe mixture was cooled down to RT
  2. filtrationfiltered on a celite pad
  3. washwashed with AcOEt (100 ml)
  4. washThe filtrate was washed with NH4Cl and saturated NaHCO3 solution and brine
  5. dry with materialThe organic phase was dried over Na2SO4
  6. customevaporated under vacuum
  7. customThe crude residue was purified by column chromatography (eluent: hexane/AcOEt 90:10 to 70:30)

出典と根拠

ORDレコード
ord-f9ad2718e899439abea27c2aeec88001
出典データセット
uspto-grants-2015_08
特許番号
US09115148B2

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