diethyl 2,3-diazabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: diethyl 2,3-diazabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate
• 英文别名: diethyl 2,3-diazabicyclo<2.2.1>hept-5-ene-2,3-dicarboxylate；2,3-diazabicyclo[2.2.1]hept-5-ene-N,N'-diethyl dicarboxylate；diethyl (1R,4S)-2,3-diazabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate
• 化学式: C₁₁H₁₆N₂O₄
• 分子量: 240.259
• InChiKey: XMAKWQGDHULQOS-DTORHVGOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  59.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl 2,3-diazabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate 以76%的产率得到
  参考文献：
  名称：

  STOUT D. M.; TAKAYA T.; MEYERS A. I., J. ORG. CHEM. , 1975, 40, NO 5, 563-569

  摘要：

  DOI：
• 作为产物：
  描述：

  环戊二烯 、 偶氮二甲酸二乙酯 以 二氯甲烷 为溶剂， 以100%的产率得到diethyl 2,3-diazabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate
  参考文献：
  名称：

  Rh（I）催化的二氮杂双环具有羰基阴离子当量的羰基开环。

  摘要：

  据报道，通过用酰基阴离子亲核试剂使中二氮杂双环开环，可对应变烯烃进行催化脱对称。立体选择性地获得密集官能化的反式1,2-肼基酰基环戊烯结构单元。酰基阴离子当量是在非常温和的条件下从容易获得的有机硼前体中原位生成的。

  DOI：

  10.1021/ol7022054

文献信息

• Rhodium(III)-Catalyzed C–H Activation/Alkylation of Diazabicyclic Olefins with Aryl Ketones: Facile Synthesis of Functionalized Cyclopentenes
  作者：K. Radhakrishnan、P. Santhini、Greeshma Gopalan、A. Smrithy

  DOI：10.1055/s-0037-1610654

  日期：2018.9

  facile synthesis of biologically important trans-functionalized cyclopentenes by a mild Rh(III)-catalyzed alkylation of strained ­diazabicyclic olefins with aryl ketones in the presence of ammonium ­acetate has been developed. The reaction proceeds through C–H bond activation of the aryl ketone groups by transforming them in to an ­autocleavable directing group, such as in situ-formed imine.

  在乙酸铵存在下，通过温和的 Rh(III) 催化烷基化与芳基酮的应变二氮杂双环烯烃，可以轻松合成具有生物学意义的反式官能化环戊烯。该反应通过芳基酮基团的 C-H 键活化进行，将它们转化为可自动裂解的导向基团，例如原位形成的亚胺。
• Rh(I)-Catalyzed Carbonylative Ring Opening of Diazabicycles with Acyl Anion Equivalents
  作者：Frederic Menard、Christian Frederik Weise、Mark Lautens

  DOI：10.1021/ol7022054

  日期：2007.12.1

  A catalytic desymmetrization of strained alkenes by ring-opening of meso-diazabicycles with acyl anion nucleophiles is reported. Densely functionalized trans-1,2-hydrazinoacyl cyclopentene building blocks are obtained stereoselectively. The acyl anion equivalent is generated in situ under very mild conditions from readily available organoboron precursors.

  据报道，通过用酰基阴离子亲核试剂使中二氮杂双环开环，可对应变烯烃进行催化脱对称。立体选择性地获得密集官能化的反式1,2-肼基酰基环戊烯结构单元。酰基阴离子当量是在非常温和的条件下从容易获得的有机硼前体中原位生成的。
• Rhodium(III)-catalyzed ring-opening of strained olefins through C–H activation of O-acetyl ketoximes: an efficient synthesis of trans-functionalized cyclopentenes and spiro[2.4]heptenes
  作者：E. Jijy、Praveen Prakash、M. Shimi、S. Saranya、P. Preethanuj、Petri M. Pihko、Sunil Varughese、K.V. Radhakrishnan

  DOI：10.1016/j.tetlet.2013.10.089

  日期：2013.12

  An efficient strategy for the stereoselective synthesis of functionalized cyclopentenes and spiro[2.4]heptenes from strained olefins via C–H activation of aryl ketone O-acetyl ketoximes using [RhCl2Cp∗]2 catalyst is described. The results revealed that a wide range of readily accessible aryl and heteroaryl ketoximes are compatible in this method for the ring opening of bicyclic and spirotricyclic olefins

  描述了一种有效的策略，可通过使用[RhCl 2 Cp ∗ ] 2催化剂通过芳基酮O-乙酰基酮肟的C–H活化，从应变烯烃立体选择性地合成官能化的环戊烯和螺[2.4]庚烯。结果表明，在该方法中，广泛存在的易于获得的芳基和杂芳基酮肟与双环和螺三环烯烃的开环相容。
• Ruthenium/Iridium-Catalyzed C-2 Activation of Indoles with Bicyclic Olefins: An Easy Access to Functionalized Heterocyclic Motifs
  作者：K. Radhakrishnan、P. Aparna、Ajesh Vijayan、Saran Raveendran、E. Suresh、R. Varma

  DOI：10.1055/s-0036-1588676

  日期：——

  Selective C-2 functionalization of N-protected and free indoles is reported. The ruthenium-catalyzed C-2 activation of indoles provided an easy access to cyclopentenylated indoles. Hydroheteroarylated bicyclic motifs were synthesized via iridium-catalyzed C-2 activation of NH indoles. The methodology was extended to different bicyclic adducts such as diaza- or urea-derived bicyclic olefins.

  报道了 N 保护和游离吲哚的选择性 C-2 功能化。钌催化的吲哚的 C-2 活化为获得环戊烯化吲哚提供了便利。氢杂芳基化双环基序是通过铱催化的 NH 吲哚的 C-2 活化合成的。该方法被扩展到不同的双环加合物，例如二氮杂或脲衍生的双环烯烃。
• Palladium-Mediated [2+1] Cycloaddition of Norbornene Derivatives with Ynamides
  作者：Hervé Clavier、Aymeric Lepronier、Nathalie Bengobesse-Mintsa、David Gatineau、Hélène Pellissier、Laurent Giordano、Alphonse Tenaglia、Gérard Buono

  DOI：10.1002/adsc.201200903

  日期：2013.2.1

  palladium-catalyzed [2+1] cycloaddition between ynamides and norbornenes or norbornadienes is reported. Both phosphapalladacycles and palladium/secondary phosphine oxide catalytic systems were found to be competent for the transformation allowing the preparation of aminomethylenecyclopropanes. The reaction showed general applicability to various functionalized bicyclo[2.2.1]hept-2-enes and ynamides. A chiral phosphapalladacycle

  报道了在酰胺和降冰片烯或降冰片二烯之间有效的钯催化的[2 + 1]环加成反应。发现磷铝环烷和钯/仲氧化膦催化体系均能胜任转化，从而可制备氨基亚甲基环丙烷。该反应显示出对各种官能化的双环[2.2.1]庚-2-烯和乙酰胺的普遍适用性。测试了手性磷酸四环四环磷酰胺以对映选择性的方式进行该转化。