1,2-Dichloroethane → ethyl 3-(3-((((3aR,4R,6R,6aS)-6-(4-((2,4-dimethoxybenzyl)amino)-7H-pyrrolo[2,3-d]pyrimidin-7-yl)-2,2-dimethyltetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl)methyl)amino)cyclobutyl)propanoate

HRID 511579

反応式

HRID 511579 の反応式
[NH2:1][CH2:2][C@@H:3]1[C@H:7]2[O:8][C:9]([CH3:12])([CH3:11])[O:10][C@H:6]2[C@H:5]([N:13]2[C:17]3[N:18]=[CH:19][N:20]=[C:21]([NH:22][CH2:23][C:24]4[CH:29]=[CH:28][C:27]([O:30][CH3:31])=[CH:26][C:25]=4[O:32][CH3:33])[C:16]=3[CH:15]=[CH:14]2)[CH2:4]1.ClCCCl.O=[C:39]1[CH2:42][CH:41]([CH2:43][CH2:44][C:45]([O:47][CH2:48][CH3:49])=[O:46])[CH2:40]1.C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(Cl)Cl>[CH3:33][O:32][C:25]1[CH:26]=[C:27]([O:30][CH3:31])[CH:28]=[CH:29][C:24]=1[CH2:23][NH:22][C:21]1[C:16]2[CH:15]=[CH:14][N:13]([C@H:5]3[C@@H:6]4[O:10][C:9]([CH3:12])([CH3:11])[O:8][C@@H:7]4[C@@H:3]([CH2:2][NH:1][CH:39]4[CH2:40][CH:41]([CH2:43][CH2:44][C:45]([O:47][CH2:48][CH3:49])=[O:46])[CH2:42]4)[CH2:4]3)[C:17]=2[N:18]=[CH:19][N:20]=1

参加物

7

反応物 5

HCID 111,2-DichloroethaneHCID 176Acetic AcidHCID 5049666Sodium triacetoxyborohydrideHCID 677749937-((3aS,4R,6R,6aR)-6-(aminomethyl)-2,2-dimethyltetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl)-N-(2,4-dimethoxybenzyl)-7H-pyrrolo[2,3-d]pyrimidin-4-amineHCID 67775333Ethyl 3-(3-oxocyclobutyl)propanoate

生成物 1

HCID 67776915ethyl 3-(3-((((3aR,4R,6R,6aS)-6-(4-((2,4-dimethoxybenzyl)amino)-7H-pyrrolo[2,3-d]pyrimidin-7-yl)-2,2-dimethyltetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl)methyl)amino)cyclobutyl)propanoate

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

A solution of 7-((3aS,4R,6R,6aR)-6-(aminomethyl)-2,2-dimethyltetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl)-N-(2,4-dimethoxybenzyl)-7H-pyrrolo[2,3-d]pyrimidin-4-amine (8.00 g, 15.2 mmol) in 1,2-Dichloroethane (119.5 mL, 1517 mmol) was treated with ethyl 3-(3-oxocyclobutyl)propanoate (2.58 g, 15.2 mmol) and Acetic acid (0.86 mL, 15 mmol) dropwise followed by Sodium triacetoxyborohydride (3.86 g, 18.2 mmol) and the mixture was stirred at RT for 19 h. The reaction mixture was diluted with 150 mL CH2Cl2 and washed with 150 mL sat NaHCO3. The aqueous phase was washed with 70 mL CH2Cl2 and the combined organic phase was dried over Na2SO4, filtered and concentrated to yield a tan glass that produced a sticky foam when placed under high vac. The crude material was purified by flash chromatography (SiO2 eluting with 3-4% 7N NH3 in CH3OH/CH2Cl2) to yield a light yellow viscous oil that producted a sticky foam under high vacuum (5.03 g). MS 608.3 (M+H).

後処理

  1. washwashed with 150 mL
  2. washThe aqueous phase was washed with 70 mL CH2Cl2
  3. dry with materialthe combined organic phase was dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto yield a tan glass that
  7. customproduced a sticky foam when
  8. customThe crude material was purified by flash chromatography (SiO2 eluting with 3-4% 7N NH3 in CH3OH/CH2Cl2)
  9. customto yield a light yellow viscous oil that

出典と根拠

ORDレコード
ord-f5717ee528334b719358810cf12d586e
出典データセット
uspto-grants-2015_08
特許番号
US09096634B2

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