[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]-(2-trimethylsilylphenyl)methanone | 194656-39-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(2S)-2-(methoxymethyl)pyrrolidin-1-yl]-(2-trimethylsilylphenyl)methanone
• CAS: 194656-39-8
• 化学式: C₁₆H₂₅NO₂Si
• 分子量: 291.466
• InChiKey: JBQZMJQCWWSCOR-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.48
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-溴乙基乙酸酯 、 [(2S)-2-(methoxymethyl)pyrrolidin-1-yl]-(2-trimethylsilylphenyl)methanone 在 间戊二烯 、 氢化钾 、 lithium bromide 、 叔丁醇 作用下， 以 四氢呋喃 、 氨 为溶剂， 反应 2.0h， 生成 Acetic acid 2-[(R)-1-((S)-2-methoxymethyl-pyrrolidine-1-carbonyl)-2-trimethylsilanyl-cyclohexa-2,5-dienyl]-ethyl ester
  参考文献：
  名称：

  Asymmetric synthesis of 4,4-disubstituted-2-cyclohexen-1-ones from a chiral 2-(trimethylsilyl)benzamide

  摘要：

  Birch reduction-alkylation of the chiral 2-(trimethylsilyl)benzamide 4 provides 1,4-cyclohexadienes 5b-5e with diastereomer ratios of >100:1. The conversions of 5b-5e to the 4,4-disubstituted-2-cyclohexen-1-ones 8b-8e are described. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01215-x
• 作为产物：
  描述：

  2-三甲基甲硅烷基苯甲酸 、 (S)-(+)-2-(甲氧基甲基)吡唑烷 以88%的产率得到[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]-(2-trimethylsilylphenyl)methanone
  参考文献：
  名称：

  Asymmetric synthesis of 4,4-disubstituted-2-cyclohexen-1-ones from a chiral 2-(trimethylsilyl)benzamide

  摘要：

  Birch reduction-alkylation of the chiral 2-(trimethylsilyl)benzamide 4 provides 1,4-cyclohexadienes 5b-5e with diastereomer ratios of >100:1. The conversions of 5b-5e to the 4,4-disubstituted-2-cyclohexen-1-ones 8b-8e are described. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01215-x

文献信息

• Desymmetrization of Benzoic Acid in the Context of the Asymmetric Birch Reduction−Alkylation Protocol. Asymmetric Total Syntheses of (−)-Eburnamonine and (−)-Aspidospermidine
  作者：Arthur G. Schultz、Liping Pettus

  DOI：10.1021/jo9707592

  日期：1997.10.1

  The highly diastereoselective potassium in ammonia reduction-ethylation (EtI) of the chiral 2-(trimethylsilyl)benzamide 1b to give 1,4-cyclohexadiene 3 is the key step in asymmetric syntheses of (-)-eburnamonine (4) and (-)-aspidospermidine (5). Cyclohexadiene 3 was converted to cyclohexanone 7, which provided the trimethylsilyl-substituted butyrolactone 9 utilized for the synthesis of 4 and butyrolactone 13 required for the synthesis of 5. The preparation of 9 depended upon the completely regioselective silicon-directed Baeyer-Villiger oxidation 7-->8; Baeyer-Villiger oxidation of the cyclohexenone 10 also was regioselective to give the desired enol lactone 11 in 92% yield. Remarkable diastereoselectivity was observed for the kinetically controlled cyclization of the acyl imminium ion derived from the vinyl-substituted carboxaldehyde 16b; treatment of 16b with 5 equiv of CF3CO2H in CH2Cl2 at -55 degrees C gave an 18:1 mixture of 17 and its C(3) beta-epimer in 93% yield. The oxidation of alcohol 18 containing sensitive indole and piperidine rings was best carried out with tetrapropylammonium perruthenate/N-methylmorpholine N-oxide to give (-)-eburnamonine (4) in 97% yield. The asymmetric synthesis of (-)-aspidospermidine 5 involved the conversion of butyrolactone 13 to the hydroxylactam 22, the Harley-Mason cyclization of 22 to 23, and reduction of 23 with LiAlH4.
• Asymmetric synthesis of 4,4-disubstituted-2-cyclohexen-1-ones from a chiral 2-(trimethylsilyl)benzamide
  作者：Arthur G. Schultz、Liping Pettus

  DOI：10.1016/s0040-4039(97)01215-x

  日期：1997.8

  Birch reduction-alkylation of the chiral 2-(trimethylsilyl)benzamide 4 provides 1,4-cyclohexadienes 5b-5e with diastereomer ratios of >100:1. The conversions of 5b-5e to the 4,4-disubstituted-2-cyclohexen-1-ones 8b-8e are described. (C) 1997 Elsevier Science Ltd.