(3R,4R)-3,4-diphenylcyclopentanone | 216223-19-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (3R,4R)-3,4-diphenylcyclopentanone
• 英文别名: (3R,4R)-3,4-diphenylcyclopentan-1-one
• CAS: 216223-19-7
• 化学式: C₁₇H₁₆O
• 分子量: 236.313
• InChiKey: HHRAKSMWUCTDPI-IRXDYDNUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (3R,4R)-3,4-diphenylcyclopentanone 在 2-氨基吡啶 、 chlorobis(ethylene)rhodium(I) dimer 、 对甲苯磺酸 、 1,3-二均三甲苯基咪唑-2-叉 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 48.0h， 以44%的产率得到(+/-)-cis-4-Oxo-1-methyl-2-phenyl-tetralin
  参考文献：
  名称：

  环戊酮中碳-碳键的催化活化

  摘要：

  在化学工业中，感兴趣的分子主要基于碳骨架。在合成此类分子时，简单底物中碳-碳单键（C-C 键）的活化具有重要的战略意义：它提供了一种断开此类惰性键的方法，形成更活跃的连接（例如，碳和过渡金属之间的连接） ) 并最终生产出更多功能的脚手架。实现这种活化的挑战在于 C-C 键的动力学惰性和新形成的碳-金属键的相对弱点。最常见的策略从三元或四元碳环系统开始，其中应变释放提供了关键的热力学驱动力。然而，基于催化活化无应变 C-C 键的广泛有用的方法已被证明难以捉摸，因为解理过程在能量上不太有利。在这里，我们报告了在简单的环戊酮和一些环己酮中催化活化 C-C 键的一般方法。我们成功的关键是铑预催化剂、N-杂环卡宾配体和氨基-吡啶助催化剂的组合。当环戊酮的 C3 位存在芳基时，可以激活应变较小的 C-C 键；随后活化芳基中的碳氢键，从而有效合成功能化的 α-四氢萘酮——有机合成中常见的结构基序和通用构

  DOI：

  10.1038/nature19849
• 作为产物：
  描述：

  (S)-N-[3-phenyl-2-(E)-propenoyl]-4-isopropyl-1,3-oxazolidine-2-thione 在 四乙基对甲苯磺酸铵 作用下， 以 乙腈 为溶剂， 生成 (3R,4R)-3,4-diphenylcyclopentanone
  参考文献：
  名称：

  Stereoselective Hydrocoupling of Optically Active 3-trans-Cinnamoyloxazolidinones by Electroreduction

  摘要：

  Reductive hydrocoupling of chiral 3-trans-cinnamoyloxazolidinones was studied by an electro chemical method. The electroreduction was performed conveniently at a constant current using an undivided cell. The stereoselectivity of the hydrodimers was strongly affected by the electrolyte employed. Electroreduction of (S)-4-isobutyl-3-trans-cinnamoyloxazolidinone 1a in 0.3 M Et4NOTs/AN gave a mixture of two diastereomers of all-trans cyclized hydrodimer 2a, and the selectivity was R,S,R/S,R,S = 85:15. On the other hand, the reduction of 1a in 1.7 M LiClO4/THF afforded a diastereomeric mixture of hydrodimers in a selectivity of R,R/S,S/R,S = 5:52:43. The stereoselectivities were explained by considering stable conformations of intermediate anion radicals, that is, syn-Z type for naked anion radicals and anti-Z type for lithiated anion radicals. Semiempirical calculations also supported this hypothesis. Electroreductions of (S)-4-isobutyl-3-cis-cinnamoyloxazolidinone and (S)-4-isobutyl-3-phenylpropioloyloxazolidinone gave 2a in the same stereoselectivity as electroreduction of 1a did. The electroreductive hydrocoupling was not inhibited by para and meta substitution on the aryl group of 3-trans-cinnamoyloxazolidinones. An ortho substitution, however, hindered the hydrocoupling and lowered the stereoselectivity of the hydrodimers. Electroreduction of 3-trans-cinnamoyloxazolidinethione and thiazolidinethione gave trans-3,4-diphenylcyclopentanone as a product, and the stereoselectivities were similar to that obtained from the corresponding oxazolidinone.

  DOI：

  10.1021/jo981231f

文献信息

• Oxidatively Initiated NHC-Catalyzed Enantioselective Synthesis of 3,4-Disubstituted Cyclopentanones from Enals
  作者：Nicholas A. White、Tomislav Rovis

  DOI：10.1021/jacs.5b06390

  日期：2015.8.19

  An unprecedented N-heterocyclic carbene (NHC)-catalyzed annulation of enals to form 3,4-disubstituted cyclopentanones has been discovered. Aryl enals undergo dimerization in the presence of a single-electron oxidant to form C2 symmetric cyclopentanones. A cross-reaction has also been developed, allowing for the synthesis of differentially substituted cyclopentanones. Mechanistically, the reaction is

  已经发现了一种前所未有的 N-杂环卡宾 (NHC) 催化的烯醛环化以形成 3,4-二取代的环戊酮。芳烯醛在单电子氧化剂存在下发生二聚反应，形成 C2 对称的环戊酮。还开发了交叉反应，允许合成差异取代的环戊酮。从机制上讲，该反应被认为是通过自由基中间体进行的，进一步确立了此类反应性的合成效用。
• MASH, EUGENE A.;HEMPERLY, SUSAN B.;NELSON, KEITH A.;HEIDT, PHILIP C.;VAN,+, J. ORG. CHEM., 55,(1990) N, C. 2045-2055
  作者：MASH, EUGENE A.、HEMPERLY, SUSAN B.、NELSON, KEITH A.、HEIDT, PHILIP C.、VAN,+

  DOI：——

  日期：——
• KREJTSBERGA YA. N.; NEJLAND O. YA.; KAMPAR V. EH., LATVRSR ZINAT. ASAD. VESTIS. KIM. SEV., IZV. AN LATVSSR. CEP. XIM., 1978,+
  作者：KREJTSBERGA YA. N.、 NEJLAND O. YA.、 KAMPAR V. EH.

  DOI：——

  日期：——