1,8-Diazabicyclo(5.4.0)undec-7-ene → 3-[(3S)-4-[4-[1-(benzyloxycarbonyl)-4-piperidyloxy]phenyl]-3-(t-butoxycarbonylamino)-1-butenyl]benzonitrile

HRID 747761ノート

反応式

HRID 747761 の反応式
[CH2:1]([O:8][C:9]([N:11]1[CH2:16][CH2:15][CH:14]([O:17][C:18]2[CH:23]=[CH:22][C:21]([CH2:24][C@H:25]([NH:30][C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[C:26](OC)=O)=[CH:20][CH:19]=2)[CH2:13][CH2:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[H-].C([Al+]CC(C)C)C(C)C.C(C(C(C([O-])=O)O)O)([O-])=O.[Na+].[K+].[Br-].[C:61]([C:63]1[CH:64]=[C:65]([CH:86]=[CH:87][CH:88]=1)[CH2:66][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)#[N:62].C1CCN2C(=NCCC2)CC1>C1(C)C=CC=CC=1.CCCCCC.C(O)C.O1CCCC1.C(OCC)(=O)C.CO>[CH2:1]([O:8][C:9]([N:11]1[CH2:12][CH2:13][CH:14]([O:17][C:18]2[CH:19]=[CH:20][C:21]([CH2:24][C@H:25]([NH:30][C:31]([O:33][C:34]([CH3:35])([CH3:37])[CH3:36])=[O:32])[CH:26]=[CH:66][C:65]3[CH:64]=[C:63]([CH:88]=[CH:87][CH:86]=3)[C:61]#[N:62])=[CH:22][CH:23]=2)[CH2:15][CH2:16]1)=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

参加物

12

反応物 5

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 2778355(3-Cyanobenzyl)triphenylphosphonium bromideHCID 9855836Potassium sodium tartarateHCID 21225700DiisobutylaluminumhydrideHCID 86760707methyl (2S)-3-[4-[1-(benzyloxycarbonyl)-4-piperidyloxy]phenyl]-2-(t-butoxycarbonylamino)propionate

生成物 1

HCID 688292673-[(3S)-4-[4-[1-(benzyloxycarbonyl)-4-piperidyloxy]phenyl]-3-(t-butoxycarbonylamino)-1-butenyl]benzonitrile

試薬・触媒・溶媒 6

HCID 702Ethanol溶媒HCID 887Methanol溶媒HCID 1140Toluene溶媒HCID 8028Tetrahydrofuran溶媒HCID 8058Hexane溶媒HCID 8857Ethyl Acetate溶媒

実験手順

3.87 g (7.70 mmol) of methyl (2S)-3-[4-[1-(benzyloxycarbonyl)-4-piperidyloxy]phenyl]-2-(t-butoxycarbonylamino)propionate was dissolved in 77 ml of toluene. 19.3 ml (19.3 mmol) of 1.0 M solution of diisobutylaluminum hydride in hexane was added to the obtained solution at −78° C., and they were stirred for 10 minutes. 10 ml of methanol and 20 ml of saturated aqueous solution of potassium sodium tartrate were added to the resultant mixture, and they were stirred at room temperature for additional one hour. After the treatment with ethyl acetate as the extractant in an ordinary manner, the obtained oily residue was dissolved in a mixed solvent of 30 ml of ethanol and 30 ml of tetrahydrofuran. After the addition of 3.53 g (7.70 mmol) of (3-cyanobenzyl)triphenylphosphonium bromide and 1.15 ml (7.70 mmol) of DBU at room temperature, the resultant mixture was stirred for one hour. The solvent was distilled off under reduced pressure, and the residue was purified by the silica gel column chromatography to obtain the title compound in the form of a mixture of geometrical isomers (E:Z=2:3).

後処理

  1. stirringwere stirred at room temperature for additional one hour
  2. distillationThe solvent was distilled off under reduced pressure
  3. customthe residue was purified by the silica gel column chromatography

出典と根拠

ORDレコード
ord-4e06595449764e2695d12705312d0ac0
出典データセット
uspto-grants-2008_07
特許番号
US07396844B1

反応ノート

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