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Citric Acid → (3aR,4R,5R,6aS)-2-oxo-4-((E)-3-oxo-4-phenoxybut-1-en-1-yl)hexahydro-2H-cyclopenta[b]furan-5-yl benzoate

HRID 561729
ノート
印刷プレビュー

反応式

HRID 561729 の反応式
[C:1]([O:9][C@@H:10]1[CH2:18][C@@H:13]2[O:14][C:15](=[O:17])[CH2:16][C@@H:12]2[C@H:11]1[CH:19]=O)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl-].[Li+].[O:23]=[C:24]([CH2:32][O:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[CH2:25]P(=O)(OC)OC.C(N(CC)CC)C.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>ClCCl.O1CCCC1>[C:1]([O:9][C@@H:10]1[CH2:18][C@@H:13]2[O:14][C:15](=[O:17])[CH2:16][C@@H:12]2[C@H:11]1/[CH:19]=[CH:25]/[C:24](=[O:23])[CH2:32][O:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

8

反応物 5

HCID 311Citric AcidHCID 8471TriethylamineHCID 433294Lithium ChlorideHCID 580104Dimethyl 2-oxo-3-phenoxypropylphosphonateHCID 11000244(3aR,4R,5R,6aS)-4-formyl-2-oxohexahydro-2H-cyclopenta[b]furan-5-yl benzoate

生成物 1

HCID 12767308
(3aR,4R,5R,6aS)-2-oxo-4-((E)-3-oxo-4-phenoxybut-1-en-1-yl)hexahydro-2H-cyclopenta[b]furan-5-yl benzoate
収率 50.6%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-20 °C

実験手順

A 4-L reactor equipped with a mechanical stirrer, under nitrogen, was charged with (3aR,4R,5R,6aS)-4-formyl-2-oxohexahydro-2H-cyclopenta[b]furan-5-yl benzoate (Cayman Chemical Catalog #70030, 99.2 g, 0.362 mol) in dichloromethane and lithium chloride (16.7 g, 0.398 mol) dissolved in tetrahydrofuran. Dimethyl 2-oxo-3-phenoxypropylphosphonate (102.7 g, 0.398 mol) is added neat and rinsed with dichloromethane (50 mL). Some lithium chloride precipitated from solution when the THF and DCM solutions were mixed. The mixture was stirred under nitrogen and cooled to −20° C. After adding the phosphonate and subsequent stirring and cooling, the precipitated lithium chloride dissolved. After stirring for 2.5 hours, triethylamine (40.2 g, 0.398 mol) was added neat via addition funnel and the temperature was held at −5° C. and stirred at this temperature for 19 hours. The temperature was adjusted to 0° C. and treated with 5% aqueous citric acid and the layers were separated. The organic layer was dried over magnesium sulfate and filtered. The crude product was purified on silica gel, eluted with ethyl acetate-hexanes (1:1). The desired product precipitated from the product-rich fractions as a white fluffy solid. After further purification of mixed fractions, all the purified product crystallized from MTBE to afford the title intermediate (74.4 g, 50.6%) as a white solid.

後処理

  1. customA 4-L reactor equipped with a mechanical stirrer, under nitrogen
  2. washrinsed with dichloromethane (50 mL)
  3. customSome lithium chloride precipitated from solution when the THF and DCM solutions
  4. additionwere mixed
  5. additionAfter adding the phosphonate
  6. stirringsubsequent stirring
  7. temperaturecooling
  8. dissolutionthe precipitated lithium chloride dissolved
  9. stirringAfter stirring for 2.5 hours
  10. customwas held at −5° C.
  11. stirringstirred at this temperature for 19 hours
  12. customwas adjusted to 0° C.
  13. customthe layers were separated
  14. dry with materialThe organic layer was dried over magnesium sulfate
  15. filtrationfiltered
  16. customThe crude product was purified on silica gel
  17. washeluted with ethyl acetate-hexanes (1:1)
  18. customThe desired product precipitated from the product-rich fractions as a white fluffy solid
  19. customAfter further purification of mixed fractions
  20. customall the purified product crystallized from MTBE

出典と根拠

ORDレコード
ord-d39d6c262c9a41c7b7e9d480cba886e8
出典データセット
uspto-grants-2011_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08063240B2

反応ノート

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