Imidazole → (-)-(1R,2S)-2-phenyl-1-cyclohexyl triisopropylsilyloxyacetate

HRID 990275

反応式

HRID 990275 の反応式
C([O:8][CH2:9][C:10](Cl)=[O:11])C1C=CC=CC=1.[C:13]1([C@@H:19]2[CH2:24][CH2:23][CH2:22][CH2:21][C@H:20]2[OH:25])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[CH:26]([Si:29](Cl)([CH:33]([CH3:35])[CH3:34])[CH:30]([CH3:32])[CH3:31])([CH3:28])[CH3:27].N1C=CN=C1>CN(C)C=O.CCCCC>[OH:11][CH2:10][C:9]([O:25][C@@H:20]1[CH2:21][CH2:22][CH2:23][CH2:24][C@H:19]1[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:8].[CH:26]([Si:29]([CH:33]([CH3:35])[CH3:34])([CH:30]([CH3:32])[CH3:31])[O:8][CH2:9][C:10]([O:25][C@@H:20]1[CH2:21][CH2:22][CH2:23][CH2:24][C@H:19]1[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:11])([CH3:28])[CH3:27]

参加物

8

反応物 4

HCID 795ImidazoleHCID 102793rel-(1R,2S)-2-PhenylcyclohexanolHCID 139400Triisopropylsilyl chlorideHCID 177085Benzyloxyacetyl chloride

生成物 2

HCID 10000489(-)-(1R,2S)-2-phenyl-1-cyclohexyl triisopropylsilyloxyacetate収率 95%HCID 10059921(-)-(1R,2S)-2-phenyl-1-cyclohexyl hydroxyacetate

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 8003Pentane溶媒

実験手順

A solution of (−)-(1R,2S)-2-phenyl-1-cyclohexyl hydroxyacetate (851 mg, 3.63 mmol) was prepared through esterification of benzyloxyacetyl chloride with (−)-(1R,2S)-2-phenyl-1-cyclohexanol followed by hydrogenolysis. Then, triisopropylsilyl chloride (840 mg, 4.36 mmol) and imidazole (618 mg, 9.08 mmol) in dimethylformamide (DMF) (1.7 mL) was added and stirred at room temperature for 12-20 hours. The mixture was poured into pentane (25 mL), and washed with water and brine. The combined organic layers were dried over anhydrous MgSO4 and concentrated in vacuo. The crude product was subjected to a purification on a short silica gel column using hexane/chloroform (3/1) as the eluant to give pure (−)-(1R,2S)-2-phenyl-1-cyclohexyl triisopropylsilyloxyacetate (1.35 g, 95% yield) as a colorless oil: [α]D20 −17.1°© 3.15, CHCl3); IR (neat) 1759, 1730 (nCO) cm−1; 1H NMR (CDCl3) δ0.93-0.99 (m, 21H), 1.30-1.62 (m, 4H), 1.72-2.0 (m, 3H), 2.10-2.19 (m, 1H), 2.66 (dt, J=11.5, 4.0 Hz, 1H), 3.90 (d, J=16.6 Hz, 1H), 4.07 (d, J=16.6 Hz, 1H), 5.07 (dt, J=10.6, 4.0 Hz, 1H), 7.16-7.30 (m, 5H). Anal. Calcd for C23H38O3Si: C, 70.72; H, 9.81. Found: C, 70.79; H, 9.85.

後処理

  1. washwashed with water and brine
  2. dry with materialThe combined organic layers were dried over anhydrous MgSO4
  3. concentrationconcentrated in vacuo
  4. customThe crude product was subjected to a purification on a short silica gel column

出典と根拠

ORDレコード
ord-4c287a8c90614d1181f10c78aa708693
出典データセット
uspto-grants-2002_10
特許番号
US06458976B1

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