Cesium carbonate → (S)-3-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-5-hydroxymethyl-oxazolidin-2-one

HRID 1890429ノート

反応式

HRID 1890429 の反応式
C([O:8][C:9](=[O:21])[NH:10][C:11]1C=CC2OCC[O:18][C:13]=2[CH:12]=1)C1C=CC=CC=1.[Li][CH2:23]CCC.[C:27]([O:32][CH2:33][C@H:34]1[O:36][CH2:35]1)(=O)[CH2:28][CH2:29][CH3:30].C([O-])([O-])=O.[Cs+].[Cs+]>C1COCC1.CC(=O)OCC>[O:32]1[C:27]2[CH:28]=[CH:29][C:30]([N:10]3[CH2:11][C@@H:12]([CH2:13][OH:18])[O:8][C:9]3=[O:21])=[CH:23][C:35]=2[O:36][CH2:34][CH2:33]1

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 6999819(S)-(+)-Glycidyl butyrateHCID 66736198(2,3-Dihydro-benzo[1,4]dioxin-6-yl)-carbamic acid benzyl esterHCID 178418339Butyllithium

生成物 1

HCID 66736976(S)-3-(2,3-dihydro-benzo[1,4]dioxin-6-yl)-5-hydroxymethyl-oxazolidin-2-one収率 62%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
-78 °C

実験手順

A solution of (2,3-dihydro-benzo[1,4]dioxin-6-yl)-carbamic acid benzyl ester (13.0 g, 45.6 mmol) in THF (220 mL) was cooled to −78° C. before the drop wise addition of n-BuLi (29.5 mL of a 2.36M solution in hexanes, 1.1 eq). The mixture was stirred at −78° C. for 1 h and then warmed to −15° C. At this temperature (S)-glycidyl butyrate (7.37 g, 1.1 eq) was added dropwise. The mixture was stirred at rt overnight. Cs2CO3 (tip of a spatula) was added and the mixture heated at 40° C. until complete conversion. The mixture was diluted with EA and washed with a sat. aq. NH4Cl and water. The org. layer was dried over MgSO4 and concentrated. The residue was purified by CC (Hex/EA 2:1, 1:1) to afford the title intermediate as a grey solid (7.04 g, 62% yield).

後処理

  1. temperaturewarmed to −15° C
  2. stirringThe mixture was stirred at rt overnight
  3. temperaturethe mixture heated at 40° C. until complete conversion
  4. washwashed with a sat. aq. NH4Cl and water
  5. dry with materiallayer was dried over MgSO4
  6. concentrationconcentrated
  7. customThe residue was purified by CC (Hex/EA 2:1, 1:1)

出典と根拠

ORDレコード
ord-4b9843c9dfc748738552f2accc94035f
出典データセット
uspto-grants-2013_08
特許番号
US08507478B2

反応ノート

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