(5R)-2-phenyl-5-methyl-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 - 苯和取代衍生物
• 英文名称: (5R)-2-phenyl-5-methyl-7-oxabicyclo[3.3.0]oct-1-en-3-one
• 英文别名: (R)-2-phenyl-5-methyl-7-oxabicyclo[3.3.0]oct-1-en-3-one；(R)-5-methyl-2-phenyl-7-oxabicyclo[3.3.0]oct-1-en-2-one；2-phenyl-5-methyl-7-oxabicyclo[3.3.0]oct-1-en-3-one；(3aR)-3a-methyl-6-phenyl-3,4-dihydro-1H-cyclopenta[c]furan-5-one
• 化学式: C₁₄H₁₄O₂
• 分子量: 214.264
• InChiKey: ZXXCEOAEQAWSPY-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 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：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (3-((2-methylallyl)oxy)prop-1-yn-1-yl)benzene 、 壬醛 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 1,4-二氧六环 为溶剂， 反应 48.0h， 以41%的产率得到(5R)-2-phenyl-5-methyl-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

• 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。
• Asymmetric Catalytic Intramolecular Pauson–Khand Reactions with Ir(phox) Catalysts
  作者：Zhong-Lin Lu、Eva Neumann、Andreas Pfaltz

  DOI：10.1002/ejoc.200700330

  日期：2007.9

  Iridium complexes derived from chiral phosphane–oxazolines (phox ligands) are efficient catalysts for intramolecular Pauson–Khand reactions. Under optimized conditions high yields and enantioselectivities of > 90 % ee were obtained with 2 mol-% of catalyst. The influence of the CO pressure and the anion were studied. The structure of a dicarbonyl(phox)iridium complex was determined by X-ray analysis

  衍生自手性磷烷-恶唑啉（phox 配体）的铱配合物是分子内 Pauson-Khand 反应的有效催化剂。在优化条件下，使用 2 mol% 的催化剂可获得高产率和 > 90% ee 的对映选择性。研究了CO压力和阴离子的影响。通过 X 射线分析确定了二羰基 (phox) 铱配合物的结构。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• 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。
• Utilization of Aldoses as a Carbonyl Source in Cyclocarbonylation of Enynes
  作者：Keiichi Ikeda、Tsumoru Morimoto、Kiyomi Kakiuchi

  DOI：10.1021/jo1012288

  日期：2010.9.17

  The reaction of enynes with acetyl-masked aldoses in the presence of a rhodium(I) catalyst resulted in cyclocarbonylation, thus avoiding the direct use of carbon monoxide, to afford bicyclic cyclopentenones. In rhodium catalysis, aldoses serve as a carbon monoxide equivalent by donating their carbonyl moieties on the acyclic aldehyde form to enynes. A variety of aldoses, including d-glucose, d-mannose

  在铑（I）催化剂存在下，烯炔与乙酰基掩盖的醛糖的反应导致环羰基化，从而避免了直接使用一氧化碳，得到双环环戊烯酮。在铑催化中，醛糖通过将其在无环醛形式上的羰基部分提供给烯炔而充当一氧化碳当量。可以使用多种醛糖，包括d-葡萄糖，d-甘露糖，d-半乳糖，d-木糖和d-核糖，作为羰基来源。使用该方法，各种烯类都以22-67％的收率被环羰基化。不对称变体也以中等至高对映选择性进行。