6-(4-trifluoromethyl-phenyl)-3a,4-dihydro-1H,3H-cyclopenta[c]furan-5-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: 6-(4-trifluoromethyl-phenyl)-3a,4-dihydro-1H,3H-cyclopenta[c]furan-5-one
• 英文别名: (R)-4-[4-(Trifluoromethyl)phenyl]-6,6aalpha-dihydro-1H-cyclopenta[c]furan-5(3H)-one；(6aR)-4-[4-(trifluoromethyl)phenyl]-1,3,6,6a-tetrahydrocyclopenta[c]furan-5-one
• 化学式: C₁₄H₁₁F₃O₂
• 分子量: 268.235
• InChiKey: DIOOTYNBRRLNFC-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 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：
  5

反应信息

• 作为产物：
  描述：

  3-(4-trifluoromethylphenyl)prop-2-yn-1-ol 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 6-(4-trifluoromethyl-phenyl)-3a,4-dihydro-1H,3H-cyclopenta[c]furan-5-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

• 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。
• 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。
• 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。
• Robust, Chiral, and Porous BINAP-Based Metal–Organic Frameworks for Highly Enantioselective Cyclization Reactions
  作者：Takahiro Sawano、Nathan C. Thacker、Zekai Lin、Alexandra R. McIsaac、Wenbin Lin

  DOI：10.1021/jacs.5b09225

  日期：2015.9.30

  We report here the design of BINAP-based metal-organic frameworks and their postsynthetic metalation with Rh complexes to afford highly active and enantioselective single-site solid catalysts for the asymmetric cyclization reactions of 1,6-enynes. Robust, chiral, and porous Zr-MOFs of UiO topology, BINAP-MOF (I) or BINAP-dMOF (II), were prepared using purely BINAP-derived dicarboxylate linkers or by

  我们在此报告了基于 BINAP 的金属有机骨架的设计及其与 Rh 配合物的合成后金属化，为 1,6-烯炔的不对称环化反应提供高活性和对映选择性的单中心固体催化剂。UiO 拓扑结构的坚固、手性和多孔 Zr-MOF，BINAP-MOF (I) 或 BINAP-dMOF (II)，分别使用纯 BINAP 衍生的二羧酸酯接头或通过将 BINAP 衍生的接头与未官能化的二羧酸酯接头混合来制备。在用 Rh(nbd)2BF4 和 [Rh(nbd)Cl]2/AgSbF6 金属化后，MOF 预催化剂 I·Rh(BF4) 和 I·Rh(SbF6) 有效地催化了高度对映选择性（高达 99% ee）的还原环化和1,6-烯炔的阿尔德烯环异构化，分别。I·Rh 催化剂在相当的对映体过量（ee' s) 和比均相对照高 4-7 倍的催化活性，这可能是 MOF 中催化位点隔离的结果，这防止了双分子催化剂失活途径。然而，I·Rh
• 2,2′‐Bis[bis(3,5‐di‐<i>tert</i>‐butyl‐4‐methoxyphenyl)phosphino]‐6,6′‐dimethoxy‐1,1′‐biphenyl in Intramolecular Rhodium(I)‐Catalyzed Asymmetric Pauson–Khand‐Type Reactions
  作者：Dong Eun Kim、Virginie Ratovelomanana‐Vidal、Nakcheol Jeong

  DOI：10.1002/adsc.201000221

  日期：2010.10.9

  AbstractA cationic rhodium(I)/2,2′‐bis[bis(3,5‐di‐tert‐butyl‐4‐methoxyphenyl)phosphino]‐6,6′‐dimethoxy‐1,1′‐biphenyl (DTBM‐MeO‐BIPHEP) catalyst was highly efficient for the asymmetric catalytic Pauson–Khand reaction, especially for those substrates containing aryl group‐substituted alkynes. The formation of the products that were derived from a β‐hydride eliminated intermediate 5 was completely suppressed over a wide range of substrates. This reaction was a serious process competing reaction with the migratory CO insertion that led to the Pauson–Khand reaction product and often substantially ruined the chemical yield of the Pauson–Khand reaction. The advantages of this system were clearly demonstrated for previously troublesome substrates, N‐tosyl‐ (1b) and malonate‐tethered 1,6‐enynes (1c), that exhibited a higher enantioselectivity without a loss in the chemical yields. The obvious beneficial effects were attributed to the synergic effect of various factors, such as the electron density of the phosphorus of the ligand, the dihedral angles of the atropisomeric ligand, and the substitution on the phosphine aryl rings which play a crucial role in the stereochemical outcome of Rh‐catalyzed Pauson–Khand reaction.