Hexamethylphosphoramide → 5-(2-Benzyloxy-ethyl)-2-oxo-cyclohexanecarboxylic acid methyl ester

HRID 133164

反応式

HRID 133164 の反応式
[Li+].CC([N-]C(C)C)C.[CH2:9]([O:16][CH2:17][CH2:18][CH:19]1[CH2:24][CH2:23][C:22](=[O:25])[CH2:21][CH2:20]1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.CN(P(N(C)C)(N(C)C)=O)C.C([C:39]([O:41][CH3:42])=[O:40])#N>C1COCC1>[CH3:42][O:41][C:39]([CH:23]1[CH2:24][CH:19]([CH2:18][CH2:17][O:16][CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH2:20][CH2:21][C:22]1=[O:25])=[O:40]

参加物

6

反応物 4

HCID 12679HexamethylphosphoramideHCID 28660Carbonocyanidic acid, methyl esterHCID 2724682Lithium diisopropylamideHCID 218796054-(2-Benzyloxyethyl)cyclohexanone

生成物 1

HCID 574432435-(2-Benzyloxy-ethyl)-2-oxo-cyclohexanecarboxylic acid methyl ester収率 90%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

A solution of LDA (33 ml, 1.5 M in Et2O) (available from Aldrich) in THF (50 mL) at −78° C. was treated with 4-(2-benzyloxy-ethyl)-cyclohexanone (9.5 g, 40.2 mmol). The mixture was warmed to 0° C. over 30 m before re-cooling to −78° C. and adding HMPA (7 mL). Methyl cyanoformate (4.1 mL, 85 mmol) (available from Aldrich) was added and the mixture was stirred for 15 m before aqueous quench and work-up. The product was purified by chromatography on SiO2 with 10% EtOAc:Hx. 5-(2-Benzyloxy-ethyl)-2-oxo-cyclohexanecarboxylic acid methyl ester was isolated, 5.8 g (49%) and reduced with an equivalent of NaBH4 in MeOH at −10° C. The alcohol (Intermediate A2) was purified by chromatography on SiO2 with 30 to 50% EtOAC:Hx. (−90% yield).

後処理

  1. temperaturebefore re-cooling to −78° C.
  2. custombefore aqueous quench
  3. customThe product was purified by chromatography on SiO2 with 10% EtOAc

出典と根拠

ORDレコード
ord-53fc676723b54bdcb3daaee9c35b50f8
出典データセット
uspto-grants-2008_06
特許番号
US07390829B2

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