3,4-Methylenedioxyphenyl-2-propanone → (2R,3S)-2-acetoxy-5,5-diethoxy-3-(3,4-methylenedioxyphenyl)pentane

HRID 263686ノート

反応式

HRID 263686 の反応式
[CH2:1]([O:3][CH:4]([O:19][CH2:20][CH3:21])[CH2:5][CH:6]([C:10]1[CH:15]=[CH:14][C:13]2[O:16][CH2:17][O:18][C:12]=2[CH:11]=1)[CH:7]([OH:9])[CH3:8])[CH3:2].C[O:23][C:24]([CH:26](C(CC(OC)=O)CC(OC)=O)CC([O-])=O)=O.C1OC2C=CC(CC(=O)C)=CC=2O1.C(OC(OCC)CI)C>C(OC=C)(=O)C.C(N(CC)CC)C>[C:24]([O:9][C@@H:7]([C@H:6]([C:10]1[CH:15]=[CH:14][C:13]2[O:16][CH2:17][O:18][C:12]=2[CH:11]=1)[CH2:5][CH:4]([O:19][CH2:20][CH3:21])[O:3][CH2:1][CH3:2])[CH3:8])(=[O:23])[CH3:26]

参加物

7

反応物 4

HCID 784073,4-Methylenedioxyphenyl-2-propanoneHCID 125047911,1-Diethoxy-2-iodoethaneHCID 18705240HCID 18705240、化合物HCID 190386566-Methyl 3-methoxycarbonyl-4-methoxycarbonylmethyladipate

生成物 1

HCID 57211167(2R,3S)-2-acetoxy-5,5-diethoxy-3-(3,4-methylenedioxyphenyl)pentane

試薬・触媒・溶媒 2

HCID 7904Vinyl Acetate溶媒HCID 8471Triethylamine溶媒

反応条件

温度
30 °C

実験手順

31.98 g of (2RS,3RS)-5,5-diethoxy-3-(3,4-methylenedioxyphenyl)pentan-2-ol [synthesized by the same method as Reference Example 1(1) and (2) using 3,4-methylenedioxyphenylacetone and iodoacetaldehyde diethyl acetal as the starting materials] was dissolved in 320 ml of vinyl acetate, and 15.1 ml of triethylamine was added thereto. Then, 1.0 g of immobilized lipase (Toyothium LIP) was added thereto, followed by stirring at 30° C. for 16 hours. Further, 0.9 g of immobilized lipase was added thereto, followed by stirring at the same temperature for 46 hours. Then, insoluble matters were filtered off. The filtrate was diluted with ethyl acetate, then sequentially washed with 1N hydrochloric acid, a saturated sodium hydrogencarbonate aqueous solution and a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. The drying agent was filtered off, and then, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=5/1→1/1) to obtain 16.05 g of the above-identified compound, [α]D20 -31.8° (c 1.0, methanol) as colorless oily substance and 18.40 g of (2R,3S)-2-acetoxy-5,5-diethoxy-3-(3,4-methylenedioxyphenyl)pentane as colorless oily substance. Further, the absolute configuration of the above-identified compound was determined by Mosher method (J. Am. Chem. Soc., vol. 113, p. 4092 (1991)).

後処理

  1. additionThen, 1.0 g of immobilized lipase (Toyothium LIP) was added
  2. additionFurther, 0.9 g of immobilized lipase was added
  3. stirringby stirring at the same temperature for 46 hours
  4. filtrationThen, insoluble matters were filtered off
  5. additionThe filtrate was diluted with ethyl acetate
  6. washsequentially washed with 1N hydrochloric acid
  7. dry with materiala saturated sodium hydrogencarbonate aqueous solution and a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate
  8. filtrationThe drying agent was filtered off
  9. distillationthe solvent was distilled off under reduced pressure
  10. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=5/1→1/1)

出典と根拠

ORDレコード
ord-92b467ab7658490eb9bda3add3192426
出典データセット
uspto-grants-1997_07
特許番号
US05643958

反応ノート

読み込み中…