1,8-Diazabicyclo(5.4.0)undec-7-ene → (7R,7aR)-4-[7-(tert-Butyldimethylsilanyloxy)-7a-methyl-1,3-dioxotetrahydropyrrolo[1,2-c]imidazol-2-yl]-2-chloro-3-methylbenzonitrile

HRID 501612ノート

反応式

HRID 501612 の反応式
CO[C:3]([C@@:5]1([CH3:25])[C@H:9]([O:10][Si:11]([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12])[CH2:8][CH2:7][N:6]1[C:18](OC(C)(C)C)=[O:19])=[O:4].CCN(C(C)C)C(C)C.[Cl:35][C:36]1[C:43]([CH3:44])=[C:42]([N:45]=C=O)[CH:41]=[CH:40][C:37]=1[C:38]#[N:39].C1CCN2C(=NCCC2)CC1>C(Cl)Cl.C(O)(C(F)(F)F)=O>[Si:11]([O:10][C@H:9]1[C@@:5]2([CH3:25])[N:6]([C:18](=[O:19])[N:45]([C:42]3[CH:41]=[CH:40][C:37]([C:38]#[N:39])=[C:36]([Cl:35])[C:43]=3[CH3:44])[C:3]2=[O:4])[CH2:7][CH2:8]1)([C:14]([CH3:15])([CH3:17])[CH3:16])([CH3:13])[CH3:12]

参加物

7

反応物 4

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 81531DiisopropylethylamineHCID 167318492-Chloro-4-isocyanato-3-methylbenzonitrileHCID 68456372(2R,3R)-3-(tert-Butyldimethylsilanyloxy)-2-methylpyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester-2-methyl ester

生成物 1

HCID 59754338(7R,7aR)-4-[7-(tert-Butyldimethylsilanyloxy)-7a-methyl-1,3-dioxotetrahydropyrrolo[1,2-c]imidazol-2-yl]-2-chloro-3-methylbenzonitrile収率 88.9%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 6422Trifluoroacetic acid溶媒

実験手順

A solution of (2R,3R)-3-(tert-Butyldimethylsilanyloxy)-2-methyl-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester-2-methyl ester (60A) (52 mg, 0.14 mmol) in CH2Cl2 (1.5 mL) and TFA (0.5 mL) was stirred at rt for 2 h. The reaction was concentrated under reduced pressure and dried under vacuum. The residue was dissolved in CH2Cl2 (1.5 mL) and Hunig's base (60 μL, 0.35 mmol) was added. After stirring at rt for 10 min, 2-chloro-4-isocyanato-3-methylbenzonitrile (34 mg, 0.18 mmol) was added and the reaction was stirred at rt overnight. The reaction was treated with DBU (40 μL, 0.27 mmol) and was stirred for 4 h at rt then concentrated under reduced pressure. The residue was purified via chromatography (silica gel) eluting with 30% EtOAc in hexane to provide the title compound (54 mg). LC/MS m/z 434 [M+H]+.

後処理

  1. concentrationThe reaction was concentrated under reduced pressure
  2. customdried under vacuum
  3. dissolutionThe residue was dissolved in CH2Cl2 (1.5 mL)
  4. stirringthe reaction was stirred at rt overnight
  5. stirringwas stirred for 4 h at rt
  6. concentrationthen concentrated under reduced pressure
  7. customThe residue was purified via chromatography (silica gel)
  8. washeluting with 30% EtOAc in hexane

出典と根拠

ORDレコード
ord-b6bcf70da0fc4a99b5266174f8ce77d3
出典データセット
uspto-grants-2010_08
特許番号
US07772267B2

反応ノート

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