cyclopropane-1,2,3-triyltris(phenylmethanone) | 2892-42-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cyclopropane-1,2,3-triyltris(phenylmethanone)
• 英文别名: (1R,2S,3S)-cyclopropane-1,2,3-triyltris(phenylmethanone)；trans-1,2,3-tribenzoylcyclopropane；1,2,3-tribenzoylcyclopropane；trans-1,2,3-Tribenzoyl-cyclopropan；trans-1.2.3-Tribenzoyl-cyclopropan
• CAS: 2892-42-4
• 化学式: C₂₄H₁₈O₃
• 分子量: 354.405
• InChiKey: CONMQAUZIMUHGB-DEVVLJCNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  27.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  51.21
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  1-苯基乙烯基硼酸 在 吡啶 、 tris(acetonitrile)pentamethylcyclopentadienylrhodium hexafluorophosphate 、 氧气 、 potassium acetate 、 copper diacetate 、 sodium sulfate 作用下， 以 2,2,2-三氟乙醇 、 1,2-二氯乙烷 为溶剂， 反应 64.0h， 生成 cyclopropane-1,2,3-triyltris(phenylmethanone)
  参考文献：
  名称：

  由 C–H 激活引发的 Rh(III)-催化的环丙烷化反应：配体开发使 N-烯氧邻苯二甲酰亚胺和烯烃的非对映选择性 [2 + 1] 环化成为可能

  摘要：

  N-烯氧基邻苯二甲酰亚胺经过 Rh(III) 催化的 C-H 活化引发缺电子烯烃的环丙烷化。建议该反应通过烯烃 C-H 键的定向活化进行，然后进行两次迁移插入，首先穿过缺电子烯烃，然后环化回烯醇部分。新设计的异丙基环戊二烯基配体极大地提高了产率和非对映选择性。

  DOI：

  10.1021/ja506579t

文献信息

• [1+1+1] Cyclotrimerization for the Synthesis of Cyclopropanes
  作者：Srimanta Manna、Andrey P. Antonchick

  DOI：10.1002/anie.201600807

  日期：2016.4.18

  The synthesis of small rings by functionalization of C(sp(3) )-H bonds remains a great challenge. We report for the first time a copper-catalyzed [1+1+1] cyclotrimerization of acetophenone derivatives under mild reaction conditions. The reaction has a broad scope for the stereoselective synthesis of cyclopropanes by trimerization of acetophenone. The developed transformation is based on an extraordinary

  通过功能化的C（sp（3））-H键合成小环仍然是一个巨大的挑战。我们首次报告在温和的反应条件下铜催化的苯乙酮衍生物的[1 + 1 + 1]环三聚。该反应对于通过苯乙酮的三聚来立体选择性地合成环丙烷具有广阔的范围。所开发的转化基于非凡的铜催化级联过程，该过程允许通过C（sp（3））-H键的官能团的环三聚作用首次获得饱和的碳环。级联的六倍C（sp（3））-H键功能化允许以高度立体选择性的方式合成环丙烷。
• Enantioselective synthesis of aroylalanine derivatives
  作者：Barry Lygo、Benjamin I. Andrews

  DOI：10.1016/s0040-4039(03)01017-7

  日期：2003.6

  paper we report the development of a highly enantioselective method for the synthesis of aroylalanines. The approach described employs a protected 2-amino-4-bromopent-4-enoic acid, generated via the asymmetric phase-transfer catalyzed alkylation of a glycine imine, as a key intermediate. Suzuki coupling with an aryl boronic acid followed by ozonolysis of the resulting styrene provides efficient access

  在本文中，我们报告了合成芳基丙氨酸的高对映选择性方法的发展。所描述的方法使用通过甘氨酸亚胺的不对称相转移催化的烷基化反应生成的受保护的2-氨基-4-溴戊-4-烯酸作为关键中间体。Suzuki与芳基硼酸偶联，然后进行臭氧氧化生成的苯乙烯，可以有效地获得芳酰丙氨酸衍生物。该方法的实用性通过1-犬尿氨酸与犬尿氨酸途径的几种芳基丙氨酸抑制剂的合成来说明。
• One-pot Synthesis of Cyclopropane Derivatives with a Cis:Trans Stereoselectivity by Wittig Olefination-Sulfur Ylide Cyclopropanation Sequence
  作者：Wenhua Huang、Lai-Ling Wang

  DOI：10.3184/174751913x13692098347208

  日期：2013.6

  Cyclopropane derivatives were synthesised in one pot from aromatic aldehydes, phenacyltriphenylphosphonium bromide, and S-phenacylthiolanium bromide by a Wittig olefination-sulfur ylide cyclopropanation sequence. When Cs2CO3 was used as the base and CH3CN/water (8:2, v/v) as the solvent, the major product was the cis-1,2-dibenzoyl cyclopropane. In contrast, when using DBU as the base and MeOH as the

  环丙烷衍生物是通过 Wittig 烯化-硫叶立德环丙烷化序列从芳香醛、苯甲酰三苯基溴化鏻和 S-苯甲酰硫基溴化鏻一锅合成的。当使用 Cs2CO3 作为碱和 CH3CN/水 (8:2, v/v) 作为溶剂时，主要产物是顺式 1,2-二苯甲酰基环丙烷。相反，当使用 DBU 作为碱和 MeOH 作为溶剂时，主要产物是反式二苯甲酰基环丙烷。在某些情况下，通过简单过滤以高纯度和高产率获得主要异构体。
• Electrophilic and nucleophilic side chain fluorination of para-substituted acetophenones
  作者：Erik Fuglseth、Thor Håkon Krane Thvedt、Maria Førde Møll、Bård Helge Hoff

  DOI：10.1016/j.tet.2008.05.060

  日期：2008.7

  para-Substituted alpha-fluoroacetophenones have been synthesised by three different routes. Electrophilic fluorination of trimethylsilyl enol ethers of acetophenones using Selectfluor (F-TEDA-BF4, 1-chloromethyl-4-fluoro- 1,4-diazoniabicyclo[ 2.2.2]octane bis-(tetrafluoroborate)) gave high to moderate yield depending on the electronic properties of the substituents. F-TEDA-BF4 mediated fluorination of acetophenones in methanol resulted in a mixture of alpha-fluoroacetophenones and the corresponding 2-fluoro- 1,1 -dimethyl acetals. The dimethyl acetals were hydrolysed using trifluoroacetic acid in water to maximise the yield of the product. Nucleophilic fluorination of alpha-bromoacetophenones using tetrabutylammoniurn hydrogen bifluoride (TBABF) led to moderate yield when having electron-donating substituents, whereas low yields were experienced when more electron-withdrawing substituents were introduced. (c) 2008 Elsevier Ltd. All rights reserved.
• Electrochemical Reduction of 2,2-Dibromoacetophenone.
  作者：Belen Batanero、Gustavo Pastor、Fructuoso Barba、Jose M. Diaz、Silvina Bassani、Hiroaki Murase、Tatsuya Shono、H. Toftlund

  DOI：10.3891/acta.chem.scand.53-0910

  日期：——

  The cathodic reduction of 2,2-dibromoacetophenone in aprotic medium DMF-LiClO4 yields (E)-4,4-dibromo-1,3-diphenyl-2,3-epoxybutan-1-one as the major product and trans-1,2,3-tribenzoylcyclopropane through an ionic or carbene route, respectively. When the electrolysis is carried out under highly dilute conditions, together with these products, (E)-4-bromo-1,3-diphenyl-2,3-epoxybutan-1-one and (Z)-4-bromo-1,3-diphenyl-2,3-epoxybutan-1-one are obtained.