Tetrahydrofuran → tert-Butyl 3,4-dihydroxypiperidine-1-carboxylate

HRID 132874

反応式

HRID 132874 の反応式
[N:1]1([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])CC=CC[CH2:2]1.Cl([O-])(=O)=[O:15].[K+].[O:19]1[CH2:23][CH2:22][CH2:21][CH2:20]1>O.[Os](=O)(=O)(=O)=O>[OH:19][CH:23]1[CH:22]([OH:15])[CH2:21][CH2:20][N:1]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH2:2]1

参加物

6

反応物 3

HCID 8028TetrahydrofuranHCID 6426889Potassium Chlorate2 回HCID 13094787tert-Butyl 3,6-dihydropyridine-1(2H)-carboxylate

生成物 1

HCID 22929427tert-Butyl 3,4-dihydroxypiperidine-1-carboxylate

試薬・触媒・溶媒 2

HCID 30318Osmium Tetroxide触媒2 回HCID 962Water溶媒2 回

反応条件

温度
80 °C

実験手順

To a stirred solution of 21 g (115 mmol) of tert-butyl 3,6-dihydropyridine-1(2H)-carboxylate from Step A in 5 mL of tetrahydrofuran was added 300 mL of water, followed by 18 g (149 mmol) of potassium chlorate. Then a solution of 200 mg of osmium tetroxide in 30 mL of water was added slowly in portions. The mixture was stirred at 80° C. for 16 h. At this time, additional portions of potassium chlorate (11.2 g, 92 mmol) and osmium tetroxide (138 mg) were added, and stirring was continued at 80° C. for another 3.5 h. The reaction mixture was partitioned between diethyl ether and water. The aqueous phase was extracted with dichloromethane and then concentrated in vacuo. The resultant residue from the aqueous phase was extracted with tetrahydrofuran. The combined organic fractions were concentrated in vacuo, and the residue was purified by flash chromatography (silica gel, 0-5% methanol/dichloromethane) to give the title compound. 1H NMR (500 MHz, CDCl3) δ 5.93 (br s, 2H), 3.92 (m, 1H)-3.83 (m, 1H), 3.63 (m, 2H), 3.39 (m, 1H), 3.25 (m, 1H), 1.84 (m, 1H), 1.72 (m, 1H), 1.47 (s, 9H). LC/MS: 240 (M+1).

後処理

  1. stirringstirring
  2. waitwas continued at 80° C. for another 3.5 h
  3. customThe reaction mixture was partitioned between diethyl ether and water
  4. extractionThe aqueous phase was extracted with dichloromethane
  5. concentrationconcentrated in vacuo
  6. extractionThe resultant residue from the aqueous phase was extracted with tetrahydrofuran
  7. concentrationThe combined organic fractions were concentrated in vacuo
  8. customthe residue was purified by flash chromatography (silica gel, 0-5% methanol/dichloromethane)

出典と根拠

ORDレコード
ord-0519e84b5b9543a68d8cf6cb537a22e7
出典データセット
uspto-grants-2008_06
特許番号
US07388019B2

関連ノート

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