2,3-Dibenzyloxycarbonyl-2,3-diazabicyclo-<2.2.1>-hepten-(5) | 49675-21-0

• 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: 2,3-Dibenzyloxycarbonyl-2,3-diazabicyclo-<2.2.1>-hepten-(5)
• 英文别名: dibenzyl 2,3-diazabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate；2,3-diaza-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid dibenzyl ester
• CAS: 49675-21-0
• 化学式: C₂₁H₂₀N₂O₄
• 分子量: 364.401
• InChiKey: KBJVVGIRURLIHX-UHFFFAOYSA-N

物化性质

• 熔点：
  92-93 °C(Solv: hexane (110-54-3))
• 沸点：
  495.6±55.0 °C(Predicted)
• 密度：
  1.314±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.24
• 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：

  2,3-Dibenzyloxycarbonyl-2,3-diazabicyclo-<2.2.1>-hepten-(5) 在 copper(I) trifluoromethanesulfonate benzene 作用下， 以 均三甲苯 为溶剂， 反应 0.08h， 以98%的产率得到benzyl (2-oxo-4,6a-dihydro-2H-cyclopenta[d][1,3]oxazol-3(3aH)-yl)carbamate
  参考文献：
  名称：

  Bifunctional Reactivity of Cu^I: Sequential Ring Opening/N-Arylation

  摘要：

  The sequential use of a single Cut catalyst enables the one-pot synthesis of N-arylaminooxazolidinones through a Lewis acid catalyzed rearrangement followed by an N-arylation reaction. Contrary to previous reports, the formation of a cis-fused 5,5-membered ring system occurs during the rearrangement, as proven by X-ray crystallography.

  DOI：

  10.1021/ol802357e
• 作为产物：
  描述：

  偶氮二甲酸二苄酯 、 环戊二烯 以 二氯甲烷 为溶剂， 以100%的产率得到2,3-Dibenzyloxycarbonyl-2,3-diazabicyclo-<2.2.1>-hepten-(5)
  参考文献：
  名称：

  Enantioselective Desymmetrization of Meso Bicyclic Hydrazines:  A Novel Approach to the Asymmetric Synthesis of Polysubstituted Amino Cyclopentanic Cores

  摘要：

  Catalytic asymmetric hydroboration can be successfully applied to meso bicyclic hydrazines. The resulting alcohols are of great synthetic interest and can lead in a straightforward manner to cyclopentanic diamino alcohols with good enantiomeric purity.

  DOI：

  10.1021/jo011190e

文献信息

• Rhodium-catalyzed enantioselective desymmetrization of bicyclic hydrazines with alkynylboronic esters
  作者：Stefano Crotti、Ferruccio Bertolini、Franco Macchia、Mauro Pineschi

  DOI：10.1039/b803693d

  日期：——

  The first successful asymmetric transfer of rhodium-alkynyl species to symmetrical strained alkenes has been realized starting from bicyclic hydrazines and alkynylboronic esters.

  从双环肼和炔基硼酸酯开始，成功实现了铑-炔基物种向对称应变烯烃的首次成功不对称转移。
• Transition metal catalyzed carboannulation of diazabicyclic alkenes with ambiphilic bifunctional reagents: a facile route towards functionalized indanones and indanols
  作者：Nayana Joseph、Jubi John、Rani Rajan、Sreeja Thulasi、Anupa Mohan、E. Suresh、K.V. Radhakrishnan

  DOI：10.1016/j.tet.2011.04.087

  日期：2011.7

  yields by the Pd/Rh catalyzed carboannulation of bicyclic and tricyclic hydrazines with 2-iodobenzonitrile, 2-cyanophenylboronic acid and 2-formylphenylboronic acid. The reaction with 2-formylphenylboronic acid afforded 3,4-disubstituted cyclopentenes as minor product along with indanones under Rh catalyzed conditions, whereas indanols were obtained as the major product under Pd catalyzed conditions. The

  通过Pd / Rh催化双环和三环肼与2-碘苄腈，2-氰基苯基硼酸和2-甲酰基苯基硼酸的碳环化反应，可以很容易地以良好的产率制备官能化的茚满酮。与2-甲酰基苯基硼酸的反应在Rh催化的条件下提供了3,4-二取代的环戊烯与茚满酮一起作为次要产物，而在Pd催化的条件下获得了作为主要产物的茚满醇。所获得的产物可以容易地合成加工成药学上重要的分子。
• A highly enantioselective catalyst for asymmetric hydroformylation of [2.2.1]-bicyclic olefins
  作者：Jinkun Huang、Emilio Bunel、Alan Allgeier、Jason Tedrow、Thomas Storz、J. Preston、Tiffany Correll、Deana Manley、Troy Soukup、Randy Jensen、Rashid Syed、George Moniz、Robert Larsen、Michael Martinelli、Paul J. Reider

  DOI：10.1016/j.tetlet.2005.09.012

  日期：2005.11

  Rh(CO)2(acac)/TangPhos was found to be a highly enantioselective catalyst for asymmetric hydroformylation of norbornylene under mild conditions. Application of the protocol to the desymmetrization of other [2.2.1]-bicyclic olefins gave moderate to excellent enantioselectivity (55–92% ee).

  发现Rh（CO）2（acac）/ TangPhos是在温和条件下降冰片烯的不对称加氢甲酰化反应的高度对映选择性催化剂。该方案在其他[2.2.1]双环烯烃的去对称化中的应用产生了中等至优异的对映选择性（55-92％ee）。
• Desymmetrization ofmeso-Bicyclic Hydrazines by Rhodium-Catalyzed Enantioselective Hydroformylation
  作者：Chloée Bournaud、Thomas Lecourt、Laurent Micouin、Catherine Méliet、Francine Agbossou-Niedercorn

  DOI：10.1002/ejoc.200800116

  日期：2008.5

  An asymmetric hydroformylation of three meso-bicyclic hydrazines followed by the reduction of the formyl product afforded the corresponding desymmetrized optically enriched hydroxymethyl hydrazines (up to 77.5 % ee). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

  三个内消旋双环肼的不对称加氢甲酰化，然后将甲酰基产物还原，得到相应的去对称的光学富集羟甲基肼（高达 77.5% ee）。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Copper-Catalysed Ring Opening of Polycyclic<i>meso</i>-Hydrazines with Trialkylaluminium Reagents and SimplePhos Ligands
  作者：Laëtitia Palais、Chloée Bournaud、Laurent Micouin、Alexandre Alexakis

  DOI：10.1002/chem.200902417

  日期：2010.2.22

  meso‐Hydrazines could be desymmetrised by ring‐opening reactions by using various metal catalysts to form substituted cyclopentenes, which have a high synthetic potential. Herein, we report the asymmetric copper‐catalysed ring opening of a range of polycyclic hydrazines with trialkylaluminium reagents and SimplePhos ligands with both high isolated yields and enantioselectivities of up to 95 %.

  通过使用各种金属催化剂形成具有高合成潜力的取代的环戊烯，可以通过开环反应来使内消旋肼脱对称。在本文中，我们报道了一系列具有三烷基铝试剂和SimplePhos配体的多环肼的不对称铜催化开环，其分离产率高，对映选择性高达95％。