Triethylamine → 11-Allyl-8-oxo-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-triene-6-carboxylic acid methyl ester

HRID 272604ノート

反応式

HRID 272604 の反応式
[CH2:1]([N:4]1[CH2:15][CH:14]2[CH2:16][CH:6]([C:7](=[O:25])[C:8]3[C:9](OS(C(F)(F)F)(=O)=O)=[CH:10][CH:11]=[CH:12][C:13]=32)[CH2:5]1)[CH:2]=[CH2:3].C(N(CC)CC)C.[C:33]([O-:36])(=[O:35])C.[K+].[CH:38]1C=CC(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>CO.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CS(C)=O>[CH3:38][O:36][C:33]([C:9]1[C:8]2[C:7](=[O:25])[CH:6]3[CH2:16][CH:14]([CH2:15][N:4]([CH2:1][CH:2]=[CH2:3])[CH2:5]3)[C:13]=2[CH:12]=[CH:11][CH:10]=1)=[O:35]

参加物

8

反応物 4

HCID 8471TriethylamineHCID 812191,3-Bis(diphenylphosphino)propaneHCID 517044Potassium AcetateHCID 59837826Trifluoro-methanesulfonic acid 11-allyl-8-oxo-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-trien-6-yl ester

生成物 1

HCID 5983784611-Allyl-8-oxo-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-triene-6-carboxylic acid methyl ester収率 569.5%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 679Dimethyl Sulfoxide溶媒HCID 887Methanol溶媒

反応条件

温度
70 °C

実験手順

Trifluoro-methanesulfonic acid 11-allyl-8-oxo-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-trien-6-yl ester (600 mg, 1.60 mmol) was dissolved in methanol (4 mL) and DMSO (10 mL) under a N2 atmosphere and treated with triethylamine (356 g, 3.5 mmol), potassium acetate (16 mg, 0.16 mmol) and 1,3-bis(diphenylphosphine)propane (66 mg, 0.16 mmol). This mixture was stirred and degassed (3 vacuum/N2 purge cycles) and then treated with palladium acetate (36 mg, 0.16 mmol). The reaction vessel was flushed with carbon monoxide for 1 minute (bubbling through a needle) then placed under the balloon. After 10 min. the mixture was warmed to 70° C. for 2 h, cooled and poured into saturated aqueous NaCl solution (50 mL). The resulting mixture was extracted with EtOAc (4×25 mL) and the combined organic layer was washed with H2O (10 mL), saturated aqueous NaHCO3 solution (10 mL) and saturated aqueous NaCl solution (10 mL), dried over MgSO4, filtered, concentrated and purified by chromatography on silica gel eluting with 50% EtOAc/hexanes to provide an oil (260 mg, 57%). (TLC 50% EtOAc/hexanes Rf 0.30); 1H NMR (400 MHz, CDCl3) δ 7.46 (d, J=7.5 Hz, 1H), 7.28 (d, J=7.5 Hz, 1H), 7.23 (dd, J=7.5, 1.3 Hz, 1H), 5.47 (m, 1H), 4.93 (m, 2H), 3.91 (s, 3H), 3.16 (dd, J=8.9, 1.6 Hz, 1H), 3.11 (d, J=1.9 Hz, 1H), 2.80 (m, 3H), 2.65 (d, J=1.7 Hz, 1H), 2.45 (dd, J=11.0, 2.5 Hz, 1H), 2.31 (m, 2H), 1.88 (ddd, J=12.8, 5.5, 2.7 Hz, 1H); GCMS m/z 285 (M)+; IR (cm−1) 2941, 2786, 1732, 1685, 1286, 1146, 1142.

後処理

  1. customdegassed
  2. custom(3 vacuum/N2 purge cycles)
  3. customThe reaction vessel was flushed with carbon monoxide for 1 minute (
  4. custombubbling through a needle)
  5. temperaturecooled
  6. additionpoured into saturated aqueous NaCl solution (50 mL)
  7. extractionThe resulting mixture was extracted with EtOAc (4×25 mL)
  8. washthe combined organic layer was washed with H2O (10 mL), saturated aqueous NaHCO3 solution (10 mL) and saturated aqueous NaCl solution (10 mL)
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. custompurified by chromatography on silica gel eluting with 50% EtOAc/hexanes

出典と根拠

ORDレコード
ord-b24348665a8842f6b17e5e8f0f464ee9
出典データセット
uspto-grants-2008_11
特許番号
US07456177B2

反応ノート

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