1-cyclohexylvinyl benzoate | 1256152-01-8

• 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: 1-cyclohexylvinyl benzoate
• 英文别名: 1-Cyclohexylvinyl benzoate；1-cyclohexylethenyl benzoate
• CAS: 1256152-01-8
• 化学式: C₁₅H₁₈O₂
• 分子量: 230.307
• InChiKey: KFQZGYXSJISICY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-cyclohexylvinyl benzoate 在 C₄₉H₆₂O₃P₂Rh⁽¹⁺⁾*BF₄^(1-) 、 氢气 作用下， 以 二氯甲烷 为溶剂， 40.0 ℃ 、400.01 kPa 条件下， 反应 24.0h， 以90%的产率得到
  参考文献：
  名称：

  Asymmetric Hydrogenation of 1-Alkyl and 1-Aryl Vinyl Benzoates: A Broad Scope Procedure for the Highly Enantioselective Synthesis of 1-Substituted Ethyl Benzoates

  摘要：

  The enantioselective hydrogenation of enol esters of formula CH2=C(OBz)R with rhodium catalysts based on phosphine phosphite ligands (P-OP) has been studied. The reaction has a broad scope, and it is suitable for the preparation of products possessing a wide variety of R substituents. For the cases where R is a primary alkyl, high catalyst activity (S/C = 500) and enantioselectivities (95-99% ee) were obtained with a catalyst characterized by an ethane backbone and a PPh2 fragment. In contrast, for R = t-Bu, a catalyst possessing a benzene backbone provided the best results (97% ee). Derivatives with a cycloalkyl R substituent were particularly difficult substrates for this reaction. A broader catalyst screening was required for these substrates, which identified a catalyst possessing a P(m-xylyl)(2) fragment as the most appropriate one, affording enantioselectivities between 90 and 95% ee. Outstanding enantioselectivities (99% ee) and high catalyst activity (S/C = 500-1000) were also obtained in the case of substrates bearing a Ph or a fluoroaryl R substituent. In addition, the system is also appropriate for the preparation of other synthetically useful esters as those for R = benzyl, 2-phenylethyl or N-phthalimido alkyl chains. Likewise, the hydrogenation of divinyl dibenzoates proceeded with very high diastero- and enantioselectivity, generating rather low amounts of the meso isomer (3-6%). On the other hand, substrates with Br and MeO substituents at the phenyl benzoate ring, suitable for further functionalization, have also been examined. The results obtained indicate no detrimental effect of these substituents in the hydrogenation. Alternatively, the methodology has been applied to the highly enantioselective synthesis of deuterium isotopomers of 1-octyl benzoate bearing CDH2, CD2H, or CD3 fragments. Finally, as a practical advantage of the present system, it has been observed that the high performance of the catalysts is retained in highly concentrated solutions or even in the neat substrate, minimizing both the amount of solvent added and the volume of the reaction.

  DOI：

  10.1021/cs501402z
• 作为产物：
  描述：

  环己基乙炔 、 苯甲酸 在 钌 作用下， 以 水 为溶剂， 反应 24.0h， 生成 1-cyclohexylvinyl benzoate
  参考文献：
  名称：

  1-烷基乙烯基苯甲酸酯的高度对映选择性加氢：手性2-烷基醇的简单，非酶促途径

  摘要：

  走向手性！描述了通过使用带有P bearingOP配体的Rh催化剂对烯醇酯1的高度对映选择性催化氢化（参见方案； NBD ＝降冰片二烯）。该催化体系具有广泛的范围，并允许制备具有高对映选择性的各种带有各种烷基或苄基的手性酯2。这些酯可以很容易地转化为高度对映体富集的2-链烷醇。

  DOI：

  10.1002/chem.201303500

文献信息

• Ruthenium(IV)-Catalyzed Markovnikov Addition of Carboxylic Acids to Terminal Alkynes in Aqueous Medium
  作者：Victorio Cadierno、Javier Francos、José Gimeno

  DOI：10.1021/om1010325

  日期：2011.2.28

  promote the selective Markovnikov addition of both aromatic and aliphatic carboxylic acids to a large variety of terminal alkynes, enynes, and diynes as well as propargylic alcohols. In this way, a wide number of enol esters and β-oxo esters could be synthesized in moderate to good yields under mild conditions (60 °C) in an aqueous medium.

  二聚的双（烯丙基）合钌（IV）配合物[的RuCl（μ-Cl）的（η 3：η 3 -C 10 ħ 16）} 2 ]（C 10 H ^ 16 = 2,7-二甲-2,6-二烯-1,8-二基）（5）和单核几个物种的反式-将[RuCl 2（η 3：η 3 -C 10 ħ 16）（L）]（L =二电子给体配体）（6）衍生的从5起已检查过使用水作为绿色反应介质将羧酸加成到末端炔烃上的催化剂。在活动和区域选择性方面的最佳结果与单核获得衍生物的反式-将[RuCl 2（η 3：η 3 -C 10 ħ 16）（PPH 3）]（6A），这是能够促进选择性Markovnikov加成芳族和脂族羧酸都可以用于各种末端炔烃，烯炔和二炔以及炔丙醇。以此方式，可以在温和条件下（60℃）在水性介质中以中等至良好的产率合成大量的烯醇酯和β-氧代酯。
• Rhodium-Catalyzed Selective <i>anti</i>-Markovnikov Addition of Carboxylic Acids to Alkynes
  作者：Alexandre Lumbroso、Nicolas R. Vautravers、Bernhard Breit

  DOI：10.1021/ol102365e

  日期：2010.12.3

  The selective intermolecular anti-Markovnikov addition of carboxylic acids to terminal alkynes yielding valuable Z-enol esters has been achieved for the first time under rhodium-catalyzed conditions. The catalyst system is applicable to a broad substrate scope and displays a wide functional group tolerance.

  在铑催化的条件下，首次实现了将羧酸选择性地分子间反Markovnikov加成到末端炔烃上，从而生成有价值的Z-烯醇酯。该催化剂体系适用于广泛的底物范围并显示出广泛的官能团耐受性。
• Highly Enantioselective Hydrogenation of 1-Alkylvinyl Benzoates: A Simple, Nonenzymatic Access to Chiral 2-Alkanols
  作者：Patryk Kleman、Pedro J. González-Liste、Sergio E. García-Garrido、Victorio Cadierno、Antonio Pizzano

  DOI：10.1002/chem.201303500

  日期：2013.11.25

  Going chiral! Highly enantioselective catalytic hydrogenations of enol esters 1 by using a Rh catalyst bearing a POP ligand are described (see scheme; NBD=norbornadiene). The catalytic system has a broad scope and allows the preparation of a wide range of chiral esters 2 bearing diverse alkyls or a benzyl group with high enantioselectivities. These esters can easily be converted in highly enantioenriched

  走向手性！描述了通过使用带有P bearingOP配体的Rh催化剂对烯醇酯1的高度对映选择性催化氢化（参见方案； NBD ＝降冰片二烯）。该催化体系具有广泛的范围，并允许制备具有高对映选择性的各种带有各种烷基或苄基的手性酯2。这些酯可以很容易地转化为高度对映体富集的2-链烷醇。
• Dehaloperoxidase Catalyzed Stereoselective Synthesis of Cyclopropanol Esters
  作者：Mary G. Siriboe、David A. Vargas、Rudi Fasan

  DOI：10.1021/acs.joc.2c02030

  日期：——

  stereoselective synthesis of these molecules remains challenging. Here, a novel strategy is reported for the diastereo- and enantioselective synthesis of cyclopropanol derivatives via the biocatalytic asymmetric cyclopropanation of vinyl esters with ethyl diazoacetate (EDA). A dehaloperoxidase enzyme from Amphitrite ornata was repurposed to catalyze this challenging cyclopropanation reaction, and its activity

  手性环丙醇是药物化学非常理想的结构单元，但这些分子的立体选择性合成仍然具有挑战性。在此，报道了一种通过乙烯基酯与重氮乙酸乙酯（EDA）的生物催化不对称环丙烷化来非对映和对映选择性合成环丙醇衍生物的新策略。来自Amphitrite ornata的脱卤过氧化物酶被重新用于催化这种具有挑战性的环丙烷化反应，并通过蛋白质工程优化了其活性和立体选择性。使用该系统，多种缺电子乙烯基酯可有效转化为所需的环丙烷化产物，非对映体和对映体比例高达 99.5:0.5。此外，基于工程脱卤过氧化物酶的生物催化剂能够催化各种其他非生物卡宾转移反应，包括用EDA插入N-H/S-H卡宾以及用重氮乙腈进行环丙烷化，从而增加了该酶的多功能性，将其定义为开发新型卡宾转移酶的有价值的新支架。
• Catalytic Asymmetric Hydrogen Atom Transfer: Enantioselective Hydroamination of Alkenes
  作者：Benjamin G. Hejna、Jacob M. Ganley、Huiling Shao、Haowen Tian、Jonathan D. Ellefsen、Nicholas J. Fastuca、Kendall N. Houk、Scott J. Miller、Robert R. Knowles

  DOI：10.1021/jacs.3c04591

  日期：2023.7.26

  report a highly enantioselective radical-based hydroamination of enol esters with sulfonamides jointly catalyzed by an Ir photocatalyst, Brønsted base, and tetrapeptide thiol. This method is demonstrated for the formation of 23 protected β-amino-alcohol products, achieving selectivities up to 97:3 er. The stereochemistry of the product is set through selective hydrogen atom transfer from the chiral

  我们报道了在 Ir 光催化剂、布朗斯台德碱和四肽硫醇的共同催化下，烯醇酯与磺酰胺发生高度对映选择性自由基加氢胺化。该方法已被证明可形成 23 种受保护的 β-氨基醇产物，选择性高达 97:3 er。产物的立体化学是通过选择性氢原子从手性硫醇催化剂转移到前手性C中心自由基来设定的。由肽催化剂和烯烃底物的结构变化衍生的结构-选择性关系为开发最佳催化剂提供了关键见解。实验和计算机制研究表明，氢键、π-π堆积和伦敦色散相互作用是底物识别和对映诱导的影响因素。这些发现进一步促进了基于自由基的不对称催化的发展，并有助于理解与此类转化相关的非共价相互作用。