Cesium carbonate → (5R)-5-[(E)-2-{5-[(1E)-4-{[tert-butyl(dimethyl)silyl]oxy}but-1-en-1-yl]-6-methoxypyridin-2-yl}-2-(4-tert-butylphenyl)ethenyl]-1-(2,4-dimethoxybenzyl)pyrrolidin-2-one

HRID 70661ノート

反応式

HRID 70661 の反応式
[O:1]([CH2:9][CH2:10]/[CH:11]=[CH:12]/B1OC(C)(C)C(C)(C)O1)[Si:2]([C:5]([CH3:8])([CH3:7])[CH3:6])([CH3:4])[CH3:3].O1C=CC=C1P(C1OC=CC=1)C1OC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+].Br[C:45]1[CH:46]=[CH:47][C:48](/[C:53](/[C:72]2[CH:77]=[CH:76][C:75]([C:78]([CH3:81])([CH3:80])[CH3:79])=[CH:74][CH:73]=2)=[CH:54]/[C@@H:55]2[N:59]([CH2:60][C:61]3[CH:66]=[CH:65][C:64]([O:67][CH3:68])=[CH:63][C:62]=3[O:69][CH3:70])[C:58](=[O:71])[CH2:57][CH2:56]2)=[N:49][C:50]=1[O:51][CH3:52]>O1CCOCC1.C(OCC)(=O)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O>[Si:2]([O:1][CH2:9][CH2:10]/[CH:11]=[CH:12]/[C:45]1[CH:46]=[CH:47][C:48](/[C:53](/[C:72]2[CH:73]=[CH:74][C:75]([C:78]([CH3:81])([CH3:80])[CH3:79])=[CH:76][CH:77]=2)=[CH:54]/[C@@H:55]2[N:59]([CH2:60][C:61]3[CH:66]=[CH:65][C:64]([O:67][CH3:68])=[CH:63][C:62]=3[O:69][CH3:70])[C:58](=[O:71])[CH2:57][CH2:56]2)=[N:49][C:50]=1[O:51][CH3:52])([C:5]([CH3:6])([CH3:7])[CH3:8])([CH3:3])[CH3:4]

参加物

9

反応物 4

HCID 10796Cesium carbonateHCID 521585Tris(furan-2-yl)phosphaneHCID 16217344(E)-tert-Butyldimethyl((4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-3-en-1-yl)oxy)silaneHCID 67397955(5R)-5-[(E)-2-(5-bromo-6-methoxypyridin-2-yl)-2-(4-tert-butylphenyl)ethenyl]-1-(2,4-dimethoxybenzyl)pyrrolidin-2-one

生成物 1

HCID 67397853(5R)-5-[(E)-2-{5-[(1E)-4-{[tert-butyl(dimethyl)silyl]oxy}but-1-en-1-yl]-6-methoxypyridin-2-yl}-2-(4-tert-butylphenyl)ethenyl]-1-(2,4-dimethoxybenzyl)pyrrolidin-2-one収率 100%

試薬・触媒・溶媒 4

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
65 °C

実験手順

trans-4-(tert-Butyldimethylsiloxy)-1-buten-1-ylboronic acid pinacol ester (296 mg), tris(dibenzylideneacetone)dipalladium(0) (48 mg), tri(2-furyl)phosphine (73 mg) and cesium carbonate (354 mg) were added to a solution of (5R)-5-[(E)-2-(5-bromo-6-methoxypyridin-2-yl)-2-(4-tert-butylphenyl)ethenyl]-1-(2,4-dimethoxybenzyl)pyrrolidin-2-one obtained in Reference Example 4-42(1) (300 mg) in 1,4-dioxane (3 mL)-water (1 mL), and the mixture was stirred at an external temperature of 65° C. for three hours. The reaction solution was left to cool, diluted with ethyl acetate and filtered through celite. The filtrate was washed with brine and dried over sodium sulfate. After filtration, the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=9:1→3:2) to give (5R)-5-[(E)-2-{5-[(1E)-4-{[tert-butyl(dimethyl)silyl]oxy}but-1-en-1-yl]-6-methoxypyridin-2-yl}-2-(4-tert-butylphenyl)ethenyl]-1-(2,4-dimethoxybenzyl)pyrrolidin-2-one as a yellow oil (399 mg, 100%).

後処理

  1. waitThe reaction solution was left
  2. temperatureto cool
  3. filtrationfiltered through celite
  4. washThe filtrate was washed with brine
  5. dry with materialdried over sodium sulfate
  6. filtrationAfter filtration
  7. customthe solvent was evaporated under reduced pressure
  8. customThe residue was purified by silica gel column chromatography (hexane:ethyl acetate=9:1→3:2)

出典と根拠

ORDレコード
ord-f7372ae500a747bfb5f028d332c9a370
出典データセット
uspto-grants-2014_09
特許番号
US08822503B2

反応ノート

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