Acetic acid 1-[2-(benzyl-trimethylsilanylmethyl-amino)-ethyl]-4-oxo-cyclohexa-2,5-dienylmethyl ester | 143957-49-7

• 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: Acetic acid 1-[2-(benzyl-trimethylsilanylmethyl-amino)-ethyl]-4-oxo-cyclohexa-2,5-dienylmethyl ester
• 英文别名: [1-[2-[Benzyl(trimethylsilylmethyl)amino]ethyl]-4-oxocyclohexa-2,5-dien-1-yl]methyl acetate
• CAS: 143957-49-7
• 化学式: C₂₂H₃₁NO₃Si
• 分子量: 385.579
• InChiKey: YBSDNXFVEIUSCS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.0
• 重原子数：
  27
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Acetic acid 1-[2-(benzyl-trimethylsilanylmethyl-amino)-ethyl]-4-oxo-cyclohexa-2,5-dienylmethyl ester 以 甲醇 为溶剂， 反应 2.0h， 以3%的产率得到Acetic acid (3aR,7aR)-1-benzyl-6-oxo-1,2,3,6,7,7a-hexahydro-indol-3a-ylmethyl 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
• 作为产物：
  描述：

  N-[(三甲基硅)甲基]苄胺 在 叔丁基过氧化氢 、 lithium aluminium tetrahydride 、 重铬酸吡啶 、 正丁基锂 、 Celite 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 29.67h， 生成 Acetic acid 1-[2-(benzyl-trimethylsilanylmethyl-amino)-ethyl]-4-oxo-cyclohexa-2,5-dienylmethyl 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

文献信息

• Exploratory studies of .alpha.-silylamino- and .alpha.-silylamido-2,5-cyclohexadien-1-one SET photochemistry. Methodology for synthesis of functionalized hydroisoquinolines
  作者：Young Shik Jung、William H. Swartz、Wei Xu、Patrick S. Mariano、Neal J. Green、Arthur G. Schultz

  DOI：10.1021/jo00048a046

  日期：1992.10

  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.