Dimethyl Sulfoxide → methyl 7-[(1R,2R,3R,5S)-5-acetoxy-2-formyl-3-(2-tetrahydropyranyl-oxy)cyclopentyl]heptanate

HRID 1943081ノート

反応式

HRID 1943081 の反応式
C(Cl)(=O)C(Cl)=O.CS(C)=O.[C:11]([O:14][C@@H:15]1[C@H:19]([CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][C:26]([O:28][CH3:29])=[O:27])[C@@H:18]([CH2:30][OH:31])[C@H:17]([O:32][CH:33]2[CH2:38][CH2:37][CH2:36][CH2:35][O:34]2)[CH2:16]1)(=[O:13])[CH3:12].C(N(CC)CC)C>ClCCl.O>[C:11]([O:14][C@@H:15]1[C@H:19]([CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][C:26]([O:28][CH3:29])=[O:27])[C@@H:18]([CH:30]=[O:31])[C@H:17]([O:32][CH:33]2[CH2:38][CH2:37][CH2:36][CH2:35][O:34]2)[CH2:16]1)(=[O:13])[CH3:12]

参加物

7

反応物 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 22789843Methyl 7-((1R,2S,3R,5S)-5-acetoxy-2-(hydroxymethyl)-3-((tetrahydro-2H-pyran-2-yl)oxy)cyclopentyl)heptanoate

生成物 1

HCID 11729034methyl 7-[(1R,2R,3R,5S)-5-acetoxy-2-formyl-3-(2-tetrahydropyranyl-oxy)cyclopentyl]heptanate収率 92.4%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6344Dichloromethane溶媒2 回

反応条件

温度
0 °C

実験手順

A solution of oxalyl chloride (28.3 ml, 324 mmol) in dichloromethane (325 ml) was cooled in a dry ice-methanol bath. Dimethylsulfoxide (46.0 ml, 648 mmol) was added drop wise and the mixture was stirred for approximately 30 minutes. A solution of methyl 7-[(1R,2S,3R,5S)-5-acetoxy-2-hydroxymethyl-3-(2-tetrahydropyranyloxy)cyclopentyl]heptanate (28) (65.00 g, 162.3 mmol) in dichloromethane (170 ml) was added thereto drop wise and the mixture was stirred for approximately 1.5 hours. Triethylamine (113 ml, 811 mmol) was added drop wise to the reaction and the reaction mixture was warmed to 0° C. Water (426 ml) was added to the reaction mixture and the mixture was stirred, let to stand and then separated into two layers. The aqueous layer was extracted twice with t-butyl methyl ether (266 ml). The organic layers were combined and sequentially washed with 1N-hydrochloric acid (390 ml), water (426 ml), saturated sodium bicarbonate water (426 ml) and saturated aqueous sodium chloride (426 ml). After drying with anhydrous magnesium sulfate (54 g), the solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (Fuji Silysia BW-300: 1950 g; ethyl acetate:hexane=3:7) to give methyl 7-[(1R,2R,3R,5S)-5-acetoxy-2-formyl-3-(2-tetrahydropyranyl-oxy)cyclopentyl]heptanate (2) (59.74 g, 149.9 mmol; yield: 92.4%) as yellow oil.

後処理

  1. stirringthe mixture was stirred for approximately 1.5 hours
  2. customwise to the reaction
  3. stirringthe mixture was stirred
  4. customseparated into two layers
  5. extractionThe aqueous layer was extracted twice with t-butyl methyl ether (266 ml)
  6. washsequentially washed with 1N-hydrochloric acid (390 ml), water (426 ml), saturated sodium bicarbonate water (426 ml) and saturated aqueous sodium chloride (426 ml)
  7. dry with materialAfter drying with anhydrous magnesium sulfate (54 g)
  8. concentrationthe solution was concentrated under reduced pressure
  9. customThe residue was purified by silica gel column chromatography (Fuji Silysia BW-300: 1950 g; ethyl acetate:hexane=3:7)

出典と根拠

ORDレコード
ord-27189eb7f1514bc39b7699bd41fa2c9c
出典データセット
uspto-grants-2013_03
特許番号
US08389748B2

反応ノート

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