Sodium Sulfite → (S)-tert-butyl 2-(5-iodo-1H-imidazol-2-yl)pyrrolidine-1-carboxylate

HRID 625557ノート

反応式

HRID 625557 の反応式
S([O-])([O-])=O.[Na+].[Na+].[I:7][C:8]1[N:9]=[C:10]([C@@H:14]2[CH2:18][CH2:17][CH2:16][N:15]2[C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[NH:11][C:12]=1I>C(O)C.O.C(OCC)(=O)C>[I:7][C:8]1[NH:9][C:10]([C@@H:14]2[CH2:18][CH2:17][CH2:16][N:15]2[C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])=[N:11][CH:12]=1

参加物

6

反応物 2

HCID 24437Sodium SulfiteHCID 59449990(S)-tert-butyl 2-(4,5-diiodo-1H-imidazol-2-yl)-pyrrolidine-1-carboxylate

生成物 1

HCID 58498756(S)-tert-butyl 2-(5-iodo-1H-imidazol-2-yl)pyrrolidine-1-carboxylate収率 73.1%

試薬・触媒・溶媒 3

HCID 702Ethanol溶媒HCID 962Water溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
90 °C

実験手順

Sodium sulfite (10.31 g, 82 mmol) was added to a solution of (S)-tert-butyl 2-(4,5-diiodo-1H-imidazol-2-yl)pyrrolidine-1-carboxylate (4.0 g, 8.2 mmol) in ethanol (75 mL) and water (75 mL). The suspension was heated with an oil bath at 100° C. for 4 hours and at 90° C. for 16 h. The reaction was diluted with ethyl acetate and water. The layers were separated and the aqueous layer was extracted several times with ethyl acetate. The combined organic phases were dried (brine, Na2SO4), filtered and concentrated in vacuo. The residue was purified by a flash chromatography (sample was dry loaded on silica gel and eluted with, 0 to 40% ethyl acetate/CH2Cl2) to afford (S)-tert-butyl 2-(5-iodo-1H-imidazol-2-yl)pyrrolidine-1-carboxylate (2.17 g, 73.1%) as a white solid. LC-MS retention time 0.930 min; calcd. for C12H181 N3O2 363.04. found m/z 364.06 [M+H]+. LC data was recorded on a Shimadzu LC-10AS liquid chromatograph equipped with a Waters Sunfire 5u C18 4.6×50 mm column using a SPD-10AV UV-Vis detector at a detector wave length of 220 nM. The elution conditions employed a flow rate of 4 mL/min, a gradient of 100% Solvent A/0% Solvent B to 0% Solvent A/100% Solvent B, a gradient time of 3 min, a hold time of 1 min and an analysis time of 4 min where Solvent A was 10% acetonitrile/90% water/0.1% TFA and Solvent B was 90% acetonitrile/10% water/0.1% TFA. 1H NMR (500 MHz, MeOD) δ ppm 7.52-7.64 (m, 1H), 4.95-5.10 (m, 1H), 3.57-3.70 (m, 1H), 3.47-3.57 (m, 1H), 2.37-2.55 (m, 1H), 1.94-2.10 (m, 3H), 1.46 (s, 4H), 1.27 (s, 5H).

後処理

  1. customThe layers were separated
  2. extractionthe aqueous layer was extracted several times with ethyl acetate
  3. dry with materialThe combined organic phases were dried (brine, Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by a flash chromatography (sample was dry loaded on silica gel and eluted with, 0 to 40% ethyl acetate/CH2Cl2)

出典と根拠

ORDレコード
ord-6c4156a7117a47db89730e8bc822bc50
出典データセット
uspto-grants-2016_04
特許番号
US09303007B2

反応ノート

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