甲基1A,6B-二氢环丙并[b]吲哚-2(1H)-羧酸酯 | 148323-46-0

• 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
• 中文名称: 甲基1A,6B-二氢环丙并[b]吲哚-2(1H)-羧酸酯
• 英文名称: 2-aza-3,4-benzo-N-carbmethoxy-bicyclo-<3.1.0>hex-3-ene
• 英文别名: 2-aza-3,4-benzo-N-carbmethoxy-bicyclo-[3.1.0]hex-3-ene；methyl 1a,6b-dihydro-1H-cyclopropa[b]indole-2-carboxylate
• CAS: 148323-46-0
• 化学式: C₁₁H₁₁NO₂
• 分子量: 189.214
• InChiKey: SYBTWSRLILYBIM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  甲基1A,6B-二氢环丙并[b]吲哚-2(1H)-羧酸酯 生成 (+)-2-aza-3,4-benzo-N-carbmethoxy-bicyclo-<3.1.0>hex-3-ene
  参考文献：
  名称：

  The effect of the benzene ring on 1,5-electrocyclizations: Synthesis and thermolysis of optically active benzohomofuran, benzohomothiophene, N-carbmethoxyhomoindole, benzohomophosphole and homoindene.

  摘要：

  Carbonyl ylide-like intermediates are involved in the 1,5-electrocyclization of the benzo-heterocycles 3a-d mentioned in the title. The activation barriers analyzed by the time- and temperature-dependence of the racemisation of the optically active derivatives turned out to be higher by DELTADELTAG(not-equal) = 13 +/- 2 kcal/mol than those determined for the parent systems 1a-d whereas for the corresponding carbocycles 3d and 1d the difference is only DELTADELTAG(not-equal) almost-equal-to 4 kcal/mol as expected from the difference between the bond dissociation energies of toluene and propene (DELTABDE = 3.2 kcal/mol). This result can be considered as an evidence for the electrocyclic character of the ring-opening in the heterocycles 1a-d and 3a-d. The difference between the Gibbs activation enthalpies found for the ring-opening of homofuran 1a and homothiophene 1b (DELTADELTAG(not-equal) = 8.7 kcal/mol) can be attributed to the heteroatom effect on the ground state.

  DOI：

  10.1016/s0957-4166(00)86091-7
• 作为产物：
  描述：

  1H-吲哚-1-羧酸甲酯 、 二碘甲烷 在 diethylzinc 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以2%的产率得到甲基1A,6B-二氢环丙并[b]吲哚-2(1H)-羧酸酯
  参考文献：
  名称：

  双核镍配合物催化还原性环丙烷化

  摘要：

  萘啶二亚胺（NDI）配体支持的双核Ni络合物以CH 2 Cl 2为亚甲基源催化烯烃的还原环丙烷化。使用温和的末端还原剂（Zn或Et 2 Zn）可赋予显着的官能团耐受性，并且该催化剂可容纳结构和电子形式多样的烯烃。带有相关N螯合物的单镍催化剂提供相对较低的环丙烷收率（≤20％）。这些结果构成了从氧化的亚甲基前体进入催化卡宾转化的进入。

  DOI：

  10.1002/anie.201511271

文献信息

• Reductive Cyclopropanations Catalyzed by Dinuclear Nickel Complexes
  作者：You-Yun Zhou、Christopher Uyeda

  DOI：10.1002/anie.201511271

  日期：2016.2.24

  Dinuclear Ni complexes supported by naphthyridine‐diimine (NDI) ligands catalyze the reductive cyclopropanation of alkenes with CH2Cl2 as the methylene source. The use of mild terminal reductants (Zn or Et2Zn) confers significant functional‐group tolerance, and the catalyst accommodates structurally and electronically diverse alkenes. Mononickel catalysts bearing related N chelates afford comparatively

  萘啶二亚胺（NDI）配体支持的双核Ni络合物以CH 2 Cl 2为亚甲基源催化烯烃的还原环丙烷化。使用温和的末端还原剂（Zn或Et 2 Zn）可赋予显着的官能团耐受性，并且该催化剂可容纳结构和电子形式多样的烯烃。带有相关N螯合物的单镍催化剂提供相对较低的环丙烷收率（≤20％）。这些结果构成了从氧化的亚甲基前体进入催化卡宾转化的进入。
• The effect of the benzene ring on 1,5-electrocyclizations: Synthesis and thermolysis of optically active benzohomofuran, benzohomothiophene, N-carbmethoxyhomoindole, benzohomophosphole and homoindene.
  作者：Frank-Gerrit Klärner、Annette E. Kleine、Dirk Oebels、Friedrich Scheidt

  DOI：10.1016/s0957-4166(00)86091-7

  日期：1993.3

  Carbonyl ylide-like intermediates are involved in the 1,5-electrocyclization of the benzo-heterocycles 3a-d mentioned in the title. The activation barriers analyzed by the time- and temperature-dependence of the racemisation of the optically active derivatives turned out to be higher by DELTADELTAG(not-equal) = 13 +/- 2 kcal/mol than those determined for the parent systems 1a-d whereas for the corresponding carbocycles 3d and 1d the difference is only DELTADELTAG(not-equal) almost-equal-to 4 kcal/mol as expected from the difference between the bond dissociation energies of toluene and propene (DELTABDE = 3.2 kcal/mol). This result can be considered as an evidence for the electrocyclic character of the ring-opening in the heterocycles 1a-d and 3a-d. The difference between the Gibbs activation enthalpies found for the ring-opening of homofuran 1a and homothiophene 1b (DELTADELTAG(not-equal) = 8.7 kcal/mol) can be attributed to the heteroatom effect on the ground state.