Benzyl Bromide → Diisopropyl (2R,3S)-2-benzyl-3-hydroxysuccinate

HRID 888211ノート

反応式

HRID 888211 の反応式
[CH:1]([O:4][C:5](=[O:15])[C@H:6]([CH2:8][C:9]([O:11][CH:12]([CH3:14])[CH3:13])=[O:10])[OH:7])([CH3:3])[CH3:2].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[CH2:26](Br)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1.[NH4+].[Cl-]>C1COCC1.O>[CH2:26]([C@H:8]([C@H:6]([OH:7])[C:5]([O:4][CH:1]([CH3:2])[CH3:3])=[O:15])[C:9]([O:11][CH:12]([CH3:14])[CH3:13])=[O:10])[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

参加物

7

反応物 4

HCID 7498Benzyl BromideHCID 25517Ammonium ChlorideHCID 2733832Lithium HexamethyldisilazideHCID 11333435Diisopropyl (S)-(-)-malate

生成物 1

HCID 14264444Diisopropyl (2R,3S)-2-benzyl-3-hydroxysuccinate収率 42.5%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
20 °C

実験手順

To a cold (−78° C.) solution of diisopropyl-(S)-(−)-malate (4.72 mL, 22.9 mmol, 1 eq.) in anhydrous THF (8.50 mL) was added slowly a solution (1 M) of lithium bis(trimethylsilyl)amide (48.1 mL, 48.1 eq., 2.10 eq.) in tetrahydrofuran. The temperature was raised to 20° C. over 30 minutes, than lowered again to −78° C. Benzyl bromide (4.70 g; 27.5 mmol; 1.20 eq.) was added and the mixture stirred at RT for 16 hours. The reaction mixture was then cooled to 0° C. and a saturated solution of NH4Cl was added. The resulting mixture was diluted with water, extracted three times with EtOAc. The combined organic layers were washed with brine and dried over MgSO4, filtered and evaporated under reduced pressure. The residue was then purified by chromatography (SiO2, 20/80 EtOAc/c-hex) to give the product as a colourless oil (3.00 g, 42%).

後処理

  1. customthan lowered again to −78° C
  2. temperatureThe reaction mixture was then cooled to 0° C.
  3. extractionextracted three times with EtOAc
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated under reduced pressure
  8. customThe residue was then purified by chromatography (SiO2, 20/80 EtOAc/c-hex)

出典と根拠

ORDレコード
ord-c3d53335d30a4a4687a146a7be2d6f73
出典データセット
uspto-grants-2012_08
特許番号
US08247437B2

反応ノート

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