(1S*,5S*,6S*)-5,7,7-trichloro-8-oxo-9-azabicyclo[4.3.0]nonane | 138816-19-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: (1S*,5S*,6S*)-5,7,7-trichloro-8-oxo-9-azabicyclo[4.3.0]nonane
• 英文别名: 3,3,4-trichlorohexahydro-1H-indol-2(3H)-one；(3aS,4S,7aS)-3,3,4-trichloro-3a,4,5,6,7,7a-hexahydro-1H-indol-2-one
• CAS: 138816-19-0
• 化学式: C₈H₁₀Cl₃NO
• 分子量: 242.532
• InChiKey: OHMHEEOTSIRCMH-HCWXCVPCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S*,5S*,6S*)-5,7,7-trichloro-8-oxo-9-azabicyclo[4.3.0]nonane 在 吡啶 作用下， 反应 3.0h， 以60%的产率得到2-吲哚酮
  参考文献：
  名称：

  Transition metal catalyzed radical cyclization: new preparative route to .gamma.-lactams from allylic alcohols via the [3.3]-sigmatropic rearrangement of allylic trichloroacetimidates and the subsequent ruthenium-catalyzed cyclization of N-allyltrichloroacetamides

  摘要：

  A sequence of reactions including [3.3]-sigmatropic rearrangement of allyl trichloroacetimidates (Overman rearrangement) followed by ruthenium-catalyzed cyclization of N-allyltrichloroacetamides provided a novel method for preparing trichlorinated gamma-lactams from allylic alcohols. No delta-lactam was formed as a byproduct. The cyclization of secondary N-allyltrichloroacetamides proceeded with good diastereoselectivity. Two types of tandem cyclizations to form bicyclic lactams took place in the cyclization of N-allyltrichloroacetamides from geraniol and linalool.

  DOI：

  10.1021/jo00032a016
• 作为产物：
  描述：

  1-(2',2',2'-trichloromethylcarbonylamino)cyclohex-2-ene 以 甲苯 为溶剂， 反应 2.0h， 以0.17 g的产率得到(1S*,5S*,6S*)-5,7,7-trichloro-8-oxo-9-azabicyclo[4.3.0]nonane
  参考文献：
  名称：

  三步串联工艺合成双环γ-内酰胺†

  摘要：

  已经开发了一种一锅三步串联方法，用于从简单的烯丙基三氯乙亚氨酸酯直接合成官能化的双环[3.3.0]，[4.3.0]和[5.3.0]γ-内酰胺。该过程涉及钯（II）介导的超人重排，随后使用Grubbs第一代复合物，该复合物既催化开环易位反应，又催化Kharasch环化。除了探索合成一系列功能化的双环γ-内酰胺的方法的范围外，手性的使用钯（II） 还证明了在对映选择性合成双环γ-内酰胺的Overman重排过程中的催化剂。

  DOI：

  10.1039/c004695g

文献信息

• Tandem Catalysis:  Generating Multiple Contiguous Carbon−Carbon Bonds through a Ruthenium-Catalyzed Ring-Closing Metathesis/Kharasch Addition
  作者：Benjamin A. Seigal、Cristina Fajardo、Marc L. Snapper

  DOI：10.1021/ja055806j

  日期：2005.11.23

  0], and [5.3.0] ring systems in one step from the appropriately functionalized acyclic precursors. For substrates where the intramolecular Kharasch addition fails, an intermolecular Kharasch addition is possible. By combining the intra- and intermolecular Kharasch additions with RCM, three new contiguous carbon-carbon bonds with multiple stereocenters can be generated by the ruthenium catalyst in a controlled

  串联催化可以提供独特而强大的策略，用于在单个反应容器中将简单的起始材料转化为更复杂的产品，同时产生更少的废物并最大限度地减少处理。在这方面，Grubbs 的亚烷基钌 (Cy3P)2Cl2Ru=CHPh 被证明可以催化两种机械上不同的转化，以提供一种独特的协议，在单个操作中影响多个键的变化。串联钌催化的烯烃闭环复分解 (RCM)/Kharasch 加成允许从适当官能化的一步中轻松制备双环 [3.3.0]、[4.3.0] 和 [5.3.0] 环系统无环前体。对于分子内哈拉施加成失败的底物，分子间哈拉施加成是可能的。通过将分子内和分子间 Kharasch 添加与 RCM 相结合，
• A three-step tandem process for the synthesis of bicyclic γ-lactams
  作者：Fiona I. McGonagle、Lindsay Brown、Andrew Cooke、Andrew Sutherland

  DOI：10.1039/c004695g

  日期：——

  A one-pot, three-step tandem process has been developed for the direct synthesis of functionalised bicyclic [3.3.0], [4.3.0] and [5.3.0] γ-lactams from simple allylic trichloroacetimidates. The process involves a palladium(II) mediated Overman rearrangement followed by the use of Grubbs first generation complex which catalyzes both a ring closing metathesis reaction and a Kharasch cyclization. As well

  已经开发了一种一锅三步串联方法，用于从简单的烯丙基三氯乙亚氨酸酯直接合成官能化的双环[3.3.0]，[4.3.0]和[5.3.0]γ-内酰胺。该过程涉及钯（II）介导的超人重排，随后使用Grubbs第一代复合物，该复合物既催化开环易位反应，又催化Kharasch环化。除了探索合成一系列功能化的双环γ-内酰胺的方法的范围外，手性的使用钯（II） 还证明了在对映选择性合成双环γ-内酰胺的Overman重排过程中的催化剂。
• Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium–arene complexes
  作者：Yannick Borguet、Xavier Sauvage、Guillermo Zaragoza、Albert Demonceau、Lionel Delaude

  DOI：10.3762/bjoc.6.133

  日期：——

  monitored by (1)H and (3)(1)P NMR spectroscopies in order to understand the intimate details of the catalytic cycles. Polyhalogenated substrates and the ethylene released upon metathesis induced the clean transformation of catalyst precursor 1 into the Ru(II)-Ru(III) mixed-valence compound [(p-cymene)Ru(mu-Cl)(3)RuCl(2)(PCy(3))], which was found to be an efficient promoter for atom transfer radical reactions

  用均双金属钌-茚基络合物[(p-cymene)Ru(mu-Cl)(3)RuCl(3-phenyl-1-indenylidene)(PCy( 3))] (1) 原位生成活性物种。这两个催化过程首先在案例研究中独立进行，然后优化整个序列并应用于从带有三卤代乙酰胺或三氯乙酸酯官能团的 α,omega-二烯底物合成几种多卤化双环 γ-内酰胺和内酯。通过 (1)H 和 (3)(1)P NMR 光谱仔细监测各个步骤，以了解催化循环的详细细节。
• Transition metal catalyzed radical cyclization: new preparative route to .gamma.-lactams from allylic alcohols via the [3.3]-sigmatropic rearrangement of allylic trichloroacetimidates and the subsequent ruthenium-catalyzed cyclization of N-allyltrichloroacetamides
  作者：Hideo Nagashima、Hidetoshi Wakamatsu、Nobuyasu Ozaki、Tsutomu Ishii、Masakazu Watanabe、Tomonori Tajima、Kenji Itoh

  DOI：10.1021/jo00032a016

  日期：1992.3

  A sequence of reactions including [3.3]-sigmatropic rearrangement of allyl trichloroacetimidates (Overman rearrangement) followed by ruthenium-catalyzed cyclization of N-allyltrichloroacetamides provided a novel method for preparing trichlorinated gamma-lactams from allylic alcohols. No delta-lactam was formed as a byproduct. The cyclization of secondary N-allyltrichloroacetamides proceeded with good diastereoselectivity. Two types of tandem cyclizations to form bicyclic lactams took place in the cyclization of N-allyltrichloroacetamides from geraniol and linalool.
• Microwave-promoted tandem reactions for the synthesis of bicyclic γ-lactams
  作者：Fiona I. McGonagle、Lindsay Brown、Andrew Cooke、Andrew Sutherland

  DOI：10.1016/j.tetlet.2011.02.089

  日期：2011.5

  A microwave-promoted three-step tandem process for the synthesis of bicyclic gamma-lactams is developed. In all cases examined this led to significantly faster tandem processes producing the bicyclic gamma-lactams more cleanly and reproducibly compared to standard thermal conditions. (C) 2011 Elsevier Ltd. All rights reserved.