4-Phenylbut-1-en-2-yl benzoate | 1255921-14-2

• 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: 4-Phenylbut-1-en-2-yl benzoate
• CAS: 1255921-14-2
• 化学式: C₁₇H₁₆O₂
• 分子量: 252.313
• InChiKey: WPFVKRHEFIVTSA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 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：

  4-Phenylbut-1-en-2-yl benzoate 在 C₄₅H₅₄O₃P₂Rh⁽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99%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：

  4-苯基-1-丁炔 、 苯甲酸 在 RuCl₂(n³:n³-2,7-dimethylocta-2,6-diene-2,8-diyl)(PPh₃) 作用下， 以 水 为溶剂， 反应 24.0h， 生成 4-Phenylbut-1-en-2-yl benzoate
  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

文献信息

• Development of an Improved Rhodium Catalyst for<i>Z</i>-Selective Anti-Markovnikov Addition of Carboxylic Acids to Terminal Alkynes
  作者：Siping Wei、Julia Pedroni、Antje Meißner、Alexandre Lumbroso、Hans-Joachim Drexler、Detlef Heller、Bernhard Breit

  DOI：10.1002/chem.201300160

  日期：2013.9.2

  To develop more active catalysts for the rhodium‐catalyzed addition of carboxylic acids to terminal alkynes furnishing anti‐Markovnikov Z enol esters, a thorough study of the rhodium complexes involved was performed. A number of rhodium complexes were characterized by NMR, ESI‐MS, and X‐ray analysis and applied as catalysts for the title reaction. The systematic investigations revealed that the presence

  为了开发更多的活性催化剂，以铑催化向末端炔烃中提供羧酸，以提供抗马尔科夫尼科夫Z烯醇酯，我们对所涉及的铑配合物进行了深入研究。通过NMR，ESI-MS和X射线分析对许多铑配合物进行了表征，并用作标题反应的催化剂。系统研究表明，氯离子的存在降低了催化剂的活性。相反，产生和应用两种铑种，即，铑[Rh（DPPMP）的混合物2 ] [H（苯甲酸酯）2 ]（DPPMP = diphenylphosphinomethylpyridine）和[的Rh（COD）（μ 2 -苯甲酸甲酯）} 2]，提供了明显更活泼的催化剂。此外，添加催化量的碱（Cs 2 CO 3）具有额外的促进作用。较高的催化剂活性使反应时间从16小时减少至1-4小时，同时保持了较高的选择性。对底物范围的研究表明，新型催化剂具有更大的官能团相容性。
• Asymmetric Hydrogenation of 1-Alkyl and 1-Aryl Vinyl Benzoates: A Broad Scope Procedure for the Highly Enantioselective Synthesis of 1-Substituted Ethyl Benzoates
  作者：Patryk Kleman、Pedro J. González-Liste、Sergio E. García-Garrido、Victorio Cadierno、Antonio Pizzano

  DOI：10.1021/cs501402z

  日期：2014.12.5

  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.