Citric Acid → 3a, 7a-Dihydroxy-octahydro-4,8-dioxa-2,6-diaza-s-indacene-2,6-dicarboxylic acid di-tert-butyl ester

HRID 2184380ノート

反応式

HRID 2184380 の反応式
CS(C)=O.[C:5]([O:9][C:10]([N:12]1[CH2:23][C:22]2([OH:24])[CH:14]([O:15][C:16]3([OH:32])[CH:20]([O:21]2)[CH2:19][N:18]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH2:17]3)[CH2:13]1)=[O:11])([CH3:8])([CH3:7])[CH3:6].C(Cl)(=O)C(Cl)=O.C(OC(N1C[C@H](O)[C@@H](O)C1)=O)(C)(C)C.C(N(CC)CC)C.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C1COCC1>[C:5]([O:9][C:10]([N:12]1[CH2:23][C:22]2([OH:24])[CH:14]([O:15][C:16]3([OH:32])[CH:20]([O:21]2)[CH2:19][N:18]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH2:17]3)[CH2:13]1)=[O:11])([CH3:8])([CH3:7])[CH3:6]

参加物

7

反応物 5

HCID 311Citric AcidHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 13329885tert-butyl (3S,4S)-3,4-dihydroxypyrrolidine-1-carboxylateHCID 86591011HCID 86591011、化合物

生成物 1

HCID 865910103a, 7a-Dihydroxy-octahydro-4,8-dioxa-2,6-diaza-s-indacene-2,6-dicarboxylic acid di-tert-butyl ester収率 20%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

3a, 7a-dihydroxy-octahydro-4,8-dioxa-2,6-diaza-s-indacene-2,6-dicarboxylic acid di-tert-butyl ester Dimethyl sulfoxide (279 μl, 3.94 mmol) was added dropwise to a stirred solution of oxalyl chloride (258 μl, 2.95 mmol) in THF (10 ml) at −78° C. After 10 min (3S,4S)-3,4-dihydroxy-pyrrolidine-1-carboxylic acid tert-butyl ester (0.5 g, 2.46 mmol) [Nagel, Angew. Chem., 96, 425 (1984)] in THF (5 ml) was added. The mixture was stirred at −78° C. for 95 min, after which triethylamine (1.7 ml, 12.3 mmol) was added. Stirring was continued for a further 20 min, after which the mixture was allowed to warm to room temperature. Citric acid (5% solution) (20 ml) was added and the mixture extracted with ethyl acetate. The organic extracts were combined, dried (MgSO4), filtered, and concentrated in vacuo then purified by flash column chromatography on silica gel, eluting with 50-70% ethyl acetate in petroleum ether to give 3a, 7a-dihydroxy-octahydro-4,8-dioxa-2,6-diaza-s-indacene-2,6-dicarboxylic acid di-tert-butyl ester (195 mg, 20%); m/z (ES+) 425 (100%, [MNa]+).

後処理

  1. stirringStirring
  2. waitwas continued for a further 20 min
  3. temperatureto warm to room temperature
  4. extractionthe mixture extracted with ethyl acetate
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customthen purified by flash column chromatography on silica gel
  9. washeluting with 50-70% ethyl acetate in petroleum ether

出典と根拠

ORDレコード
ord-cdaecb4014c74cdaacd1858c1c25f030
出典データセット
uspto-grants-2005_05
特許番号
US06900345B2

反応ノート

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