diethyl 2-methyl-3-oxobicyclo[3.3.0]oct-1-ene-7,7-dicarboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: diethyl 2-methyl-3-oxobicyclo[3.3.0]oct-1-ene-7,7-dicarboxylate
• 英文别名: diethyl (3aR)-6-methyl-5-oxo-1,3,3a,4-tetrahydropentalene-2,2-dicarboxylate
• 化学式: C₁₅H₂₀O₅
• 分子量: 280.321
• InChiKey: KJRHDHISTICOGE-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  烯丙基丙二酸二乙酯 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 sodium hydride 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 53.0h， 生成 diethyl 2-methyl-3-oxobicyclo[3.3.0]oct-1-ene-7,7-dicarboxylate
  参考文献：
  名称：

  Iridium-catalyzed cascade decarbonylation/highly enantioselective Pauson–Khand-type cyclization reactions

  摘要：

  An easily accessible chiral iridium-BINAP complex can effect the cooperative processes of decarbonylation of an aldehyde and cascaded enantioselective Pauson-Khand-type reaction. A survey of ligands revealed that atropisomeric aryl-diphosphine ligands were superior to chiral alkyl-diphosphines in this dual catalysis. Applying the reaction conditions of [IrCl(COD)](2)/(S)-BINAP complex with nonylaldehyde as a CO surrogate at 100 degrees C in anhydrous dioxane solvent, various 1,6-enynes were transformed to the corresponding optically active bicyclic cyclopentenones with excellent enantioselectivities (up to 98% ee). (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.03.036

文献信息

• Formate as a CO surrogate for cascade processes: Rh-catalyzed cooperative decarbonylation and asymmetric Pauson–Khand-type cyclization reactions
  作者：Hang Wai Lee、Albert S. C. Chan、Fuk Yee Kwong

  DOI：10.1039/b702718d

  日期：——

  A rhodium-(S)-xyl-BINAP complex-catalyzed tandem formate decarbonylation and [2 + 2 + 1] carbonylative cyclization is described; this cooperative process utilizes formate as a condensed CO source, and the newly developed cascade protocol can be extended to its enantioselective version, providing up to 94% ee of the cyclopentenone adducts.

  介绍了铑-(S)-xyl-BINAP配合物催化的甲酸脱羰和[2 + 2 + 1]羰基化环化联用反应；这种协同过程利用甲酸作为浓缩的CO源，新开发的级联方案可以扩展到其对映选择性版本，提供的环戊烯酮加成物的对映体过量值高达94%。
• Rhodium-BisbenzodioxanPhos Complex-Catalyzed Homogeneous Enantioselective Pauson-Khand-Type Cyclization in Alcoholic Solvents
  作者：Fuk Yee Kwong、Hang Wai Lee、Liqin Qiu、Wai Har Lam、Yue-Ming Li、Hoi Lun Kwong、Albert S. C. Chan

  DOI：10.1002/adsc.200505105

  日期：2005.11

  s was found to be highly effective in the co-operative processeses of aldehyde decarbonylation and cascaded enantioselective Pauson–Khand-type reactions. Various 1,6-enynes were transformed to the corresponding bicyclic cyclopentenones in good yields and enantiomeric excesses (up to 96% ee). The attractive feature of this new Rh-catalyzed homogeneous dual catalysis system is that the reaction can be

  发现手性阻转异构二膦配体（S）-双苯并二恶烷膦在醛脱羰和级联对映选择性Pauson-Khand型反应的合作过程中非常有效。各种1,6-烯炔以良好的收率和对映体过量（最高ee为96％）转化为相应的双环环戊烯酮。这种新的Rh催化均相双重催化系统的吸引人之处在于该反应可以在酒精溶液中进行。
• Rhodium-Catalyzed Asymmetric Aqueous Pauson-Khand-Type Reaction
  作者：Fuk Yee Kwong、Yue Ming Li、Wai Har Lam、Liqin Qiu、Hang Wai Lee、Chi Hung Yeung、Kin Shing Chan、Albert S. C. Chan

  DOI：10.1002/chem.200401237

  日期：2005.6.20

  operationally simple protocol allows both catalyst and reactants to be handled under air without precautions. Various enynes were transformed to the corresponding bicyclic cyclopentenones in good yield and enantiomeric excess (up to 95 % ee). A study of the electronic effects of the enyne substrates revealed a correlation between the electronic properties of the substrates and the ee value obtained in

  开发了一种有趣的铑催化的不对称含水Pauson-Khand型反应。发现手性阻转异构体二吡啶基二膦配体在该系统中是高度有效的。该操作简单的方案允许催化剂和反应物都在空气中进行处理而无需采取预防措施。将各种烯炔以良好的收率和对映体过量（至多95％ee）转化为相应的双环环戊烯酮。对烯炔底物的电子效应的研究表明，底物的电子性质与Pauson-Khand型反应产物中获得的ee值之间存在相关性。从Hammett研究中观察到线性自由能关系。
• Microwave‐Assisted Rhodium‐Complex‐Catalyzed Cascade Decarbonylation and Asymmetric Pauson–Khand‐Type Cycli­zations
  作者：Hang Wai Lee、Lai Na Lee、Albert S. C. Chan、Fuk Yee Kwong

  DOI：10.1002/ejoc.200800272

  日期：2008.7

  Microwave-assisted Rh–diphosphane-complex-catalyzed dual catalysis is reported. This cooperative process provides [2+2+1] cycloadducts by sequential decarbonylation of aldehyde or formate and carbonylation of enynes within a short period of time. Various O-, N-, and C-tethered enynes were transformed into the corresponding products in good yields. The first enantioselective version of this microwave-accelerated

  报道了微波辅助的 Rh-二膦复合物催化的双催化。这种协同过程通过醛或甲酸酯的顺序脱羰和烯炔的羰基化在短时间内提供 [2+2+1] 环加合物。各种O-、N-和C-系链烯炔以良好的产率转化为相应的产品。实现了这种微波加速级联环化的第一个对映选择性版本。在手性 Rh-(S)-bisbenzodioxanPhos 络合物的存在下，环戊烯酮产品的 ee 值高达 90%。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Immobilized Co/Rh Heterobimetallic Nanoparticle-Catalyzed Pauson-Khand-Type Reaction
  作者：Kang Hyun Park、Young Keun Chung

  DOI：10.1002/adsc.200404298

  日期：2005.5

  Co/Rh heterobimetallic nanoparticles were prepared from cobalt-rhodium carbonyl clusters [Co2Rh2(CO)12 and Co3Rh(CO)12] and immobilized on charcoal. HR-TEM revealed that the size of the heterobimetallic nanoparticles was ca. 2 nm and ICP-AES analysis showed a 2 : 2 and a 3 : 1 cobalt-rhodium stoichiometry (Co2Rh2 and Co3Rh1) in the heterobimetallic nanoparticles. The Co/Rh heterobimetallic nanoparticles

  由钴铑羰基簇[Co 2 Rh 2（CO）12和Co 3 Rh（CO）12 ]制备Co / Rh异质双金属纳米颗粒，并将其固定在木炭上。HR-TEM显示，杂双金属纳米粒子的大小约为。2 nm和ICP-AES分析显示钴铑化学计量比为2：2和3：1（Co 2 Rh 2和Co 3 Rh 1）在异双金属纳米粒子中。固定在木炭上的Co / Rh异双金属纳米颗粒在1atm的CO下用作Pauson-Khand型反应的催化剂。催化反应活性高度依赖于Co：Rh的比率，当该比率最高时，观察到最高的反应活性。为2：2（Co 2 Rh 2）。Co 2 Rh 2固定化催化剂对于分子内和分子间的Pauson-Khand型反应是非常有效的催化剂。固定化Co 2 Rh 2时在醛而不是一氧化碳的存在下，Pauson-Khand型反应中，该催化剂被用作催化剂，该催化体系非常有效。当反应在手性二膦的存在下进行时，观察到ee值高达