2-(4-methylphenyl)-7-oxabicyclo[3.3.0]oct-1-en-3-one | 1042670-82-5

• 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-(4-methylphenyl)-7-oxabicyclo[3.3.0]oct-1-en-3-one
• 英文别名: 3a,4-dihydro-6-(4-methylphenyl)-1H-cyclopenta[c]furan-5(3H)-one；2-(4-Methylphenyl)-7-oxabicyclo[3.3.0]oct-1-en-3-one；4-(4-methylphenyl)-1,3,6,6a-tetrahydrocyclopenta[c]furan-5-one
• CAS: 1042670-82-5
• 化学式: C₁₄H₁₄O₂
• 分子量: 214.264
• InChiKey: ITTYFJIAEVEVOX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 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-(4-甲基苯基)-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-methylphenyl)-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

• 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)
• Rh-Catalyzed Aqueous Pauson-Khand-Type Cycloaddition in Microwave-Irradiated Medium
  作者：Fuk Kwong、Albert Chan、Hang Lee

  DOI：10.1055/s-2008-1078413

  日期：2008.6

  Microwave-assisted Rh-catalyzed dual catalysis in aqueous medium is described. This tandem process transforms the enyne to cycloadduct by cascade decarbonylation of formate ester and subsequently carbonylation of enyne under microwave-irradiated conditions.

  描述了一种微波辅助的铑催化双重催化反应，应用于水相介质。该串联过程通过对甲酸酯的级联脱羧和随后在微波辐照条件下对烯炔的羰基化，将烯炔转化为环加成产物。
• 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。
• Rhodium-Catalyzed Asymmetric Pauson-Khand Reaction Using Monophosphoramidite Ligand SIPHOS
  作者：Bao-Min Fan、Jian-Hua Xie、Shen Li、Yong-Qiang Tu、Qi-Lin Zhou

  DOI：10.1002/adsc.200404395

  日期：2005.5

  A novel rhodium-catalyzed asymmetric intramolecular Pauson–Khand reaction using a chiral monophosphoramidite ligands is described. In this reaction, an in situ generated catalyst from [Rh(CO)2Cl]2, the spiro-monophosphoramidite ligand SIPHOS and AgSbF6 was found to be effective for a series of 1,6-enynes, providing the co-cyclization products in good enantioselectivities (84% ee).

  描述了一种使用手性单亚磷酰胺配体的新型铑催化的不对称分子内Pauson-Khand反应。在该反应中，发现由[Rh（CO）2 Cl] 2，螺-单亚磷酰胺基配体SIPHOS和AgSbF 6原位生成的催化剂对一系列1,6-烯炔有效，可提供共环化产物具有良好的对映选择性（84％ee）。