(Z)-ethyl 3-cyclohexylbut-2-enoate | 73232-03-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (Z)-ethyl 3-cyclohexylbut-2-enoate
• 英文别名: ethyl (Z)-3-cyclohexyl-2-butenoate；Ethyl 3-cyclohexylbut-2-enoate；(E)-ethyl 3-cyclohexylbut-2-enoate；ethyl (2Z)-3-cyclohexylbut-2-enoate；ethyl (Z)-3-cyclohexylbut-2-enoate
• CAS: 73232-03-8
• 化学式: C₁₂H₂₀O₂
• 分子量: 196.29
• InChiKey: QYHINSWQNUZZDQ-KTKRTIGZSA-N

物化性质

• 沸点：
  264.3±9.0 °C(Predicted)
• 密度：
  0.964±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  (Z)-ethyl 3-cyclohexylbut-2-enoate 在 二异丁基氢化铝 作用下， 以 二氯甲烷 为溶剂， 反应 1.57h， 以94%的产率得到(Z)-3-cyclohexylbut-2-en-1-ol
  参考文献：
  名称：

  基于辅助SN2'反应的四元立体中心的不对称构建：1,7-相对立体形成的案例

  摘要：

  The stereoselective construction of quaternary stereogenic centers is described that employs an allylic substitution through the intermediacy of a chiral carbamate leaving group. Five carbamates with two substituents at the allylic terminus combined with phenylcopper or n-butylcopper to provide alkenes in moderate to good yields and with moderate to high enantioselectivities at the newly created quaternary stereogenic center. The E-carbamate with methyl and cyclohexyl substituents at the gamma-terminus provided the highest yield (87%) and enantioselectivity (>99.9:0.1 er) of all the substitution patterns tested. The corresponding Z-carbamate gave the lowest enantioselectivity observed (80.0:20.0). Carbamates with other substituents (n-butyl and t-butyl) at the E-terminal position gave moderate yields and enantioselectivities of alkenes. Cinnamyl substrates also provided good yields of alkenes with moderate enantioselectivities. The origin of enantioselectivity is analyzed in the context of dimeric lithioheterocuprate structures.

  DOI：

  10.3987/com-13-s(s)82
• 作为产物：
  描述：

  乙酰基环己烷 在 锌 、 三氯氧磷 作用下， 以 氯仿 、 苯 为溶剂， 反应 14.0h， 生成 (Z)-ethyl 3-cyclohexylbut-2-enoate
  参考文献：
  名称：

  基于辅助SN2'反应的四元立体中心的不对称构建：1,7-相对立体形成的案例

  摘要：

  The stereoselective construction of quaternary stereogenic centers is described that employs an allylic substitution through the intermediacy of a chiral carbamate leaving group. Five carbamates with two substituents at the allylic terminus combined with phenylcopper or n-butylcopper to provide alkenes in moderate to good yields and with moderate to high enantioselectivities at the newly created quaternary stereogenic center. The E-carbamate with methyl and cyclohexyl substituents at the gamma-terminus provided the highest yield (87%) and enantioselectivity (>99.9:0.1 er) of all the substitution patterns tested. The corresponding Z-carbamate gave the lowest enantioselectivity observed (80.0:20.0). Carbamates with other substituents (n-butyl and t-butyl) at the E-terminal position gave moderate yields and enantioselectivities of alkenes. Cinnamyl substrates also provided good yields of alkenes with moderate enantioselectivities. The origin of enantioselectivity is analyzed in the context of dimeric lithioheterocuprate structures.

  DOI：

  10.3987/com-13-s(s)82

文献信息

• Highly Enantioselective Iridium-Catalyzed Hydrogenation of α,β-Unsaturated Esters
  作者：Jia-Qi Li、Xu Quan、Pher G. Andersson

  DOI：10.1002/chem.201200907

  日期：2012.8.20

  α,β‐Unsaturated esters have been employed as substrates in iridium‐catalyzed asymmetric hydrogenation. Full conversions and good to excellent enantioselectivities (up to 99 % ee) were obtained for a broad range of substrates with both aromatic‐ and aliphatic substituents on the prochiral carbon. The hydrogenated products are highly useful as building blocks in the synthesis of a variety of natural

  在铱催化的不对称氢化反应中，α，β-不饱和酯已被用作底物。对于在手性碳上同时具有芳族和脂族取代基的多种底物，可实现完全转化和良好至优异的对映选择性（高达99％  ee）。氢化产物在多种天然产物和药物的合成中作为构建基非常有用。
• Asymmetric Conjugate Reduction of α,β-Unsaturated Ketones and Esters with Chiral Rhodium(2,6-bisoxazolinylphenyl) Catalysts
  作者：Yoshinori Kanazawa、Yasunori Tsuchiya、Kazuki Kobayashi、Takushi Shiomi、Jun-ichi Itoh、Makoto Kikuchi、Yoshihiko Yamamoto、Hisao Nishiyama

  DOI：10.1002/chem.200500841

  日期：2006.1

  New asymmetric conjugate reduction of beta,beta-disubstituted alpha,beta-unsaturated ketones and esters was accomplished with alkoxylhydrosilanes in the presence of chiral rhodium(2,6-bisoxazolinylphenyl) complexes in high yields and high enantioselectivity. (E)-4-Phenyl-3-penten-2-one and (E)-4-phenyl-4-isopropyl-3-penten-2-one were readily reduced at 60 degrees C in 95 % ee and 98 % ee, respectively

  在手性铑（2,6-双恶唑啉基苯基）络合物的存在下，用烷氧基氢硅烷以高收率和高对映选择性完成了β，β-二取代的α，β-不饱和酮和酯的新的不对称共轭还原。（E）-4-苯基-3-戊烯-2-酮和（E）-4-苯基-4-异丙基-3-戊烯-2-酮在60°C下容易在95％ee和98％ee中还原分别以1 mol％的催化剂负载量进行。（EtO）2MeSiH被证明是最佳的氢供体选择。（E）-β-甲基肉桂酸叔丁酯和β-异丙基肉桂酸酯也可以还原为相应的二氢肉桂酸酯衍生物，直到ee高达98％。
• Enantioselective Intramolecular Aldehyde α-Alkylation with Simple Olefins: Direct Access to Homo-Ene Products
  作者：Robert J. Comito、Fernanda G. Finelli、David W. C. MacMillan

  DOI：10.1021/ja4047312

  日期：2013.6.26

  A highly selective method for the synthesis of asymmetrically substituted carbocycles and heterocycles from unactivated aldehyde-olefin precursors has been achieved via enantioselective SOMO-catalysis. Addition of a catalytically generated enamine radical cation across a pendent olefin serves to establish a general asymmetric strategy toward the production of a wide range of formyl-substituted rings

  通过对映选择性 SOMO 催化，实现了一种从未活化的醛-烯烃前体合成不对称取代的碳环和杂环的高选择性方法。在悬垂烯烃上添加催化生成的烯胺自由基阳离子有助于建立一般的不对称策略，以产生广泛的具有烯烃转位的甲酰基取代的环。从概念上讲，这种新颖的机制允许直接访问“均烯”型产品。
• Asymmetric 1,4-reductions of and 1,4-additions to enoates and related systems
  申请人：——

  公开号：US20030125563A1

  公开（公告）日：2003-07-03

  One aspect of the present invention relates to methods for the transition-metal-catalyzed asymmetric 1,4-addition of a nucleophile, e.g., hydride, to cyclic and acyclic enoates and enones. In certain embodiments of the methods of the present invention, the transition metal catalyst consists essentially of copper and an asymmetric bidentate bisphosphine ligand.

  本发明的一个方面涉及过渡金属催化的手性1,4-加成方法，用于将亲核试剂（例如氢化物）加成到环状和非环状烯酸酯和烯酮上。在本发明的某些实施方式中，过渡金属催化剂基本上由铜和手性双膦配体组成。
• Iridium-Catalyzed Asymmetric Isomerization of Primary Allylic Alcohols
  作者：Luca Mantilli、David Gérard、Sonya Torche、Céline Besnard、Clément Mazet

  DOI：10.1002/anie.200901863

  日期：2009.6.29

  AbstractNothing to sm(Ir)k at: Under appropriate reaction conditions, iridium hydride catalysts promote the isomerization of primary allylic alcohols. The best catalysts, like (R)‐1 (P green, O red, N blue, Ir yellow), deliver the desired chiral aldehydes with excellent enantioselectivity and good yields. Mechanistic hypotheses have been developed on the basis of preliminary investigations.magnified image