2-(4-methoxyphenyl)-7-oxabicyclo[3.3.0]oct-1-en-3-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-(4-methoxyphenyl)-7-oxabicyclo[3.3.0]oct-1-en-3-one
• 英文别名: (6aS)-4-(4-methoxyphenyl)-1,3,6,6a-tetrahydrocyclopenta[c]furan-5-one
• 化学式: C₁₄H₁₄O₃
• 分子量: 230.263
• InChiKey: KNSRQSKERYFNHG-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  3-(4-甲氧基苯基)-2-丙炔-1-醇 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 48.0h， 生成 2-(4-methoxyphenyl)-7-oxabicyclo[3.3.0]oct-1-en-3-one
  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-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。
• Electronic and Steric Effects of Atropisomeric Ligands SYNPHOS® and DIFLUORPHOS®vs. BINAPs in Rh(I)-Catalyzed Asymmetric Pauson–Khand Reaction
  作者：Dong Eun Kim、Choong Choi、In Su Kim、Séverine Jeulin、Virginie Ratovelomanana-Vidal、Jean-Pierre Genêt、Nakcheol Jeong

  DOI：10.1002/adsc.200600623

  日期：2007.8.6

  electronic and steric effects of chiral biaryl diphosphine ligands on the Rh(I)-catalyzed asymmetric Pauson–Khand type reaction were examined. We demonstrated that enantioselectivity and reaction yield were influenced by the electronic density on phosphorus, the dihedral angle of ligands and the electronic density of the alkyne substrate. Ligands bearing a narrower dihedral angle than Binap, such as Synphos

  检查了手性联芳基二膦配体对Rh（I）催化的不对称Pauson-Khand型反应的电子和空间效应。我们证明对映选择性和反应产率受磷的电子密度，配体的二面角和炔烃底物的电子密度的影响。与Binap型配体相比，发现具有比Binap窄的二面角的配体，例如Synphos（L4）和Difluorphos（L5），大大提高了反应的对映选择性。具有去屏蔽的膦的配体，例如p -CF 3 -Binap（L3）和Difluorphos（L5）提供了比Binap更好的对映选择性，并减少了副产物的形成，特别是对于电子贫乏的炔烃底物。
• Iridium-catalyzed enantioselective Pauson–Khand-type reaction of 1,6-enynes
  作者：Takanori Shibata、Natsuko Toshida、Mitsunori Yamasaki、Shunsuke Maekawa、Kentaro Takagi

  DOI：10.1016/j.tet.2005.08.016

  日期：2005.10

  Iridium–chiral diphosphine complex catalyzes an enantioselective intramolecular Pauson–Khand-type reaction to give various chiral bicyclic cyclopentenones. The enantioselective reaction proceeds more smoothly and enantioselectively under a lower partial pressure of carbon monoxide. Moreover, aldehyde can be used as a CO source in the enantioselective carbonylative coupling.

  铱-手性二膦配合物催化对映选择性分子内Pauson-Khand型反应，生成各种手性双环环戊烯酮。在较低的一氧化碳分压下，对映选择性反应更平稳和对映选择性地进行。此外，在对映选择性羰基化偶联中，可以将醛用作CO源。
• The Electronic Effect of Ligands on Stereoselectivity in the Rhodium(I)-Catalyzed Asymmetric Pauson-Khand-Type Reaction under a Carbon Monoxide Atmosphere
  作者：Virginie Ratovelomanana-Vidal、Jean-Pierre Genêt、Nakcheol Jeong、Dong Kim、Choong Choi、In Kim、Séverine Jeulin

  DOI：10.1055/s-2006-950369

  日期：2006.12

  of various ligands on the stereoselectivity and reaction rate of the rhodium(I)-catalyzed asymmetric Pauson-Khand-type reaction were examined. We demonstrated that both the reaction rate and the enantioselectivity are significantly dependent on the electron density of the ligands; when ligands bearing deshielded phosphine were utilized, the reaction rate was slower, but the products were obtained with

  基于所提出的机理，研究了各种配体对铑(I)催化的不对称Pauson-Khand型反应的立体选择性和反应速率的电子效应。我们证明了反应速率和对映选择性都显着依赖于配体的电子密度。当使用带有去屏蔽膦的配体时，反应速度较慢，但​​得到的产物对映选择性有所提高。