(8R,8aR)-8-(tert-Butyl-dimethyl-silanyloxymethyl)-octahydro-indolizine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 英文名称: (8R,8aR)-8-(tert-Butyl-dimethyl-silanyloxymethyl)-octahydro-indolizine
• 英文别名: [(8R,8aR)-1,2,3,5,6,7,8,8a-octahydroindolizin-8-yl]methoxy-tert-butyl-dimethylsilane
• 化学式: C₁₅H₃₁NOSi
• 分子量: 269.503
• InChiKey: LICXBWWQTOLFDG-UONOGXRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.88
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (8R,8aR)-8-(tert-Butyl-dimethyl-silanyloxymethyl)-octahydro-indolizine 在 草酰氯 、 四丁基氟化铵 、 对甲苯磺酸 、 二甲基亚砜 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 34.75h， 生成 8-[1-Piperidin-1-yl-meth-(E)-ylidene]-octahydro-indolizine
  参考文献：
  名称：

  Heterocycle Formation through Aza-Annulation: Stereochemically Controlled Syntheses of (.+-.)-5-Epitashiromine and (.+-.)-Tashiromine

  摘要：

  N-alkylenamines, stabilized through conjugation with an electron-withdrawing group, undergo aza-annulation with acryloyl chloride to provide a convergent route for the construction of six-membered nitrogen heterocycles. In addition to enhancing the C-alkylation process of annulation relative to the competing N-acylation process, the electron withdrawing substituent controlled the regioselectivity of alkene formation in both the intermediate enamine and in the unsaturated lactam product. A variety of functional groups, which include -COMe, -COPh, -CO(2)R, -CONHPh, -CN, -P(O)(OEt)(2), and -SO(2)Ph, were used to determine the effect of the electron-withdrawing substituents upon both the annulation reaction with acryloyl chloride and the subsequent hydrogenation process. When the enamide annulation product was stabilized through conjugation with ester or amide substituents, catalytic hydrogenation of the ate-annulation product resulted in the formation of vicinal stereocenters with high cis selectivity. The utility of this methodology was demonstrated by application of the condensation/aza-annulation/hydrogenation sequence as the key for construction and stereochemical control of the indolizidine ring system of (+/-)-tashiromine.

  DOI：

  10.1021/jo00086a009
• 作为产物：
  描述：

  6-(苄氧基)-3-氧代己酸乙酯 在 palladium on activated charcoal 咪唑 、 lithium aluminium tetrahydride 、 四溴化碳 、 氢气 、 lithium 、 sodium carbonate 、 对甲苯磺酸 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 氨 、 N,N-二甲基甲酰胺 、 苯 为溶剂， -33.0~25.0 ℃ 、303.98 kPa 条件下， 反应 52.0h， 生成 (8R,8aR)-8-(tert-Butyl-dimethyl-silanyloxymethyl)-octahydro-indolizine
  参考文献：
  名称：

  Heterocycle Formation through Aza-Annulation: Stereochemically Controlled Syntheses of (.+-.)-5-Epitashiromine and (.+-.)-Tashiromine

  摘要：

  N-alkylenamines, stabilized through conjugation with an electron-withdrawing group, undergo aza-annulation with acryloyl chloride to provide a convergent route for the construction of six-membered nitrogen heterocycles. In addition to enhancing the C-alkylation process of annulation relative to the competing N-acylation process, the electron withdrawing substituent controlled the regioselectivity of alkene formation in both the intermediate enamine and in the unsaturated lactam product. A variety of functional groups, which include -COMe, -COPh, -CO(2)R, -CONHPh, -CN, -P(O)(OEt)(2), and -SO(2)Ph, were used to determine the effect of the electron-withdrawing substituents upon both the annulation reaction with acryloyl chloride and the subsequent hydrogenation process. When the enamide annulation product was stabilized through conjugation with ester or amide substituents, catalytic hydrogenation of the ate-annulation product resulted in the formation of vicinal stereocenters with high cis selectivity. The utility of this methodology was demonstrated by application of the condensation/aza-annulation/hydrogenation sequence as the key for construction and stereochemical control of the indolizidine ring system of (+/-)-tashiromine.

  DOI：

  10.1021/jo00086a009

文献信息

• Heterocycle Formation through Aza-Annulation: Stereochemically Controlled Syntheses of (.+-.)-5-Epitashiromine and (.+-.)-Tashiromine
  作者：K. Paulvannan、John R. Stille

  DOI：10.1021/jo00086a009

  日期：1994.4

  N-alkylenamines, stabilized through conjugation with an electron-withdrawing group, undergo aza-annulation with acryloyl chloride to provide a convergent route for the construction of six-membered nitrogen heterocycles. In addition to enhancing the C-alkylation process of annulation relative to the competing N-acylation process, the electron withdrawing substituent controlled the regioselectivity of alkene formation in both the intermediate enamine and in the unsaturated lactam product. A variety of functional groups, which include -COMe, -COPh, -CO(2)R, -CONHPh, -CN, -P(O)(OEt)(2), and -SO(2)Ph, were used to determine the effect of the electron-withdrawing substituents upon both the annulation reaction with acryloyl chloride and the subsequent hydrogenation process. When the enamide annulation product was stabilized through conjugation with ester or amide substituents, catalytic hydrogenation of the ate-annulation product resulted in the formation of vicinal stereocenters with high cis selectivity. The utility of this methodology was demonstrated by application of the condensation/aza-annulation/hydrogenation sequence as the key for construction and stereochemical control of the indolizidine ring system of (+/-)-tashiromine.