1-[(Benzyl-trimethylsilanylmethyl-carbamoyl)-methyl]-2-methoxy-4-oxo-cyclohexa-2,5-dienecarboxylic acid methyl ester | 143925-58-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1-[(Benzyl-trimethylsilanylmethyl-carbamoyl)-methyl]-2-methoxy-4-oxo-cyclohexa-2,5-dienecarboxylic acid methyl ester
• 英文别名: Methyl 1-[2-[benzyl(trimethylsilylmethyl)amino]-2-oxoethyl]-2-methoxy-4-oxocyclohexa-2,5-diene-1-carboxylate
• CAS: 143925-58-0
• 化学式: C₂₂H₂₉NO₅Si
• 分子量: 415.561
• InChiKey: SXQJSICMJCYYQU-UHFFFAOYSA-N

物化性质

• 沸点：
  555.6±50.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.11
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  72.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-[(Benzyl-trimethylsilanylmethyl-carbamoyl)-methyl]-2-methoxy-4-oxo-cyclohexa-2,5-dienecarboxylic acid methyl ester 以 乙腈 为溶剂， 反应 8.0h， 生成 6-[(Benzyl-trimethylsilanylmethyl-carbamoyl)-methyl]-2-methoxy-4-oxo-bicyclo[3.1.0]hex-2-ene-6-carboxylic acid methyl ester
  参考文献：
  名称：

  Exploratory studies of .alpha.-silylamino- and .alpha.-silylamido-2,5-cyclohexadien-1-one SET photochemistry. Methodology for synthesis of functionalized hydroisoquinolines

  摘要：

  The electron-transfer (SET) photochemistry of selected alpha-silylamino and alpha-silylamido 2,5-cyclohexadienones has been explored with the intent of developing a novel and potentially efficient method for functionalized hydroisoquinoline synthesis. These substances, prepared by Birch reduction-alkylation-oxidation sequences, were found to undergo 9,10-dicyanoanthracene-SET-sensitized radical cyclization to form hydroisoquinolines in a highly regio- and stereoselective fashion and in modest to good yields. In contrast, the major direct irradiation reaction pathway followed by the alpha-silylamido-substituted systems involves type A rearrangement to bicyclic cyclohexenones or phenols. Direct irradiation of the alpha-silylamino analogs, on the other hand, brings about near-exclusive conversion to the corresponding hydroisoquinolines. The synthetic and mechanistic features of this study are described.

  DOI：

  10.1021/jo00048a046