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Triphenylphosphine → 6-(2,2-Diphenyl-ethylamino)-9-((1R,4S)-4-hydroxy-cyclopent-2-enyl)-9H-purine-2-carboxylic acid methyl ester

HRID 1882580
ノート
印刷プレビュー

反応式

HRID 1882580 の反応式
[CH3:1][O:2][C:3]([C:5]1[N:13]=[C:12]2[C:8]([N:9]=[CH:10][NH:11]2)=[C:7]([NH:14][CH2:15][CH:16]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[N:6]=1)=[O:4].[H-].[Na+].CC([O:34][C@H:35]1[CH:39]=[CH:38][C@@H:37](O)[CH2:36]1)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:1][O:2][C:3]([C:5]1[N:13]=[C:12]2[C:8]([N:9]=[CH:10][N:11]2[C@@H:38]2[CH2:39][C@H:35]([OH:34])[CH:36]=[CH:37]2)=[C:7]([NH:14][CH2:15][CH:16]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[N:6]=1)=[O:4]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

6

反応物 4

HCID 11776TriphenylphosphineHCID 24758Sodium hydrideHCID 10154103rac-(1R,4S)-4-hydroxycyclopent-2-en-1-yl acetateHCID 178418823HCID 178418823、化合物

生成物 1

HCID 666305706-(2,2-Diphenyl-ethylamino)-9-((1R,4S)-4-hydroxy-cyclopent-2-enyl)-9H-purine-2-carboxylic acid methyl ester

試薬・触媒・溶媒 1

HCID 9811564
Bis(dibenzylideneacetone)palladium
触媒

反応条件

温度
40 °C

実験手順

To 6-(2,2-diphenyl-ethylamino)-9H-purine-2-carboxylic acid methyl ester (5 g 13.4 mmol) under an atmosphere of argon is added dry deoxygenated tetrahydrofuran (100 ml) and dry dimethyl sulfoxide (2 ml). Sodium hydride 95% (0.32 g, 13.4 mmol) is then added and the solution is stirred at 40° C. Separately to (1S,4R)-cis 4-Acetoxy-2-cyclopenten-1-ol (1.89 g. 13.4 mmol), triphenylphosphine (0.53 g, 2.0 mmol) and tris(dibenzylideneacetone)dipalladium(0) (0.69 g, 0.67 mmol) is added dry deoxygenated tetrahydrofuran (20 ml) and the mixture stirred at room temperature for 10 minutes. This solution is added to the anion solution via syringe and the resulting mixture is then stirred at 80° C. The reaction is shown to be complete by LCMS after 2 hours. The reaction mixture is allowed to cool, methanol is added and a solid is filtered. The filtrate is concentrated in vacuo and the title compound is obtained by precipitation from dichloromethane/hexane. 1H NMR (MeOD, 400 MHz); 8.15 (s, 1H), 7.40-7.15 (m, 10H), 6.20 (m, 1H), 5.95 (m, 1H), 5.50 (m, 2H), 4.75 (m, 2H), 4.55 (m, 1H), 4.10 (m 2H), 3.90 (s, 2H), 3.80 (s, 1H), 2.9 (m, 1H), 1.75 (m, 1H).

後処理

  1. customdry
  2. customdeoxygenated tetrahydrofuran (100 ml) and dry dimethyl sulfoxide (2 ml)
  3. customdry
  4. customdeoxygenated tetrahydrofuran (20 ml)
  5. stirringthe mixture stirred at room temperature for 10 minutes
  6. additionThis solution is added to the anion solution via syringe
  7. stirringthe resulting mixture is then stirred at 80° C
  8. temperatureto cool
  9. additionmethanol is added
  10. filtrationa solid is filtered
  11. concentrationThe filtrate is concentrated in vacuo

出典と根拠

ORDレコード
ord-7a9d21aa900844029f104e857d572d4a
出典データセット
uspto-grants-2012_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08318750B2

反応ノート

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