methyl (S)-3-cyclohexyl-3-hydroxy-2-methylenepropanoate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: methyl (S)-3-cyclohexyl-3-hydroxy-2-methylenepropanoate
• 英文别名: methyl 2-(cyclohexyl(hydroxy)methyl)acrylate；methyl 2-[(S)-cyclohexyl(hydroxy)methyl]prop-2-enoate
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: AYGWIGMHORVIRU-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,4,6-三甲基苯甲腈N-氧化物 、 methyl (S)-3-cyclohexyl-3-hydroxy-2-methylenepropanoate 以 甲苯 为溶剂， 反应 3.0h， 生成 (1'R*,5R*) methyl 5-(1-hydroxy-1-cyclohexylmethyl)-3-(2,4,6-trimethylphenyl)isoxazoline-5-carboxylate 、 (1'S*,5R*) methyl 5-(1-hydroxy-1-cyclohexylmethyl)-3-(2,4,6-trimethylphenyl)isoxazoline-5-carboxylate
  参考文献：
  名称：

  Reversal of Diastereoselectivity of Nitrile Oxide 1,3-Dipolar Cycloadditions by Mg(II). Acceleration of Cycloaddition by Microwave Irradiation

  摘要：

  1,3-Dipolar cycloadditions of mesitonitrile oxide to Baylis-Hillman adducts (beta-hydroxy-alpha-methylene esters) proceed regioselectively in good yields. Addition of Grignard reagent reverses the diastereoselectivity of the cycloaddition. Microwave irradiation strongly accelerates the reaction with only a small effect on its diastereoisomeric excess. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00454-3
• 作为产物：
  描述：

  环己烷基甲醛 在 α-isocupreine 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 13.5h， 生成 methyl (S)-3-cyclohexyl-3-hydroxy-2-methylenepropanoate
  参考文献：
  名称：

  α‐Isocupreine，β‐Isocupreidine的对映体互补催化剂

  摘要：

  互补化学！通过CF 3 SO 3 H处理，从奎宁一步一步合成了α-异cupreine（α-ICPN）（参见方案）。在Morita-Baylis-Hillman反应中，该化合物可作为β-异cupreidine（β-ICD）的对映体互补催化剂。

  DOI：

  10.1002/chem.201302665

文献信息

• Asymmetric Morita-Baylis-Hillman Reaction: Catalyst Development and Mechanistic Insights Based on Mass Spectrometric Back-Reaction Screening
  作者：Patrick G. Isenegger、Florian Bächle、Andreas Pfaltz

  DOI：10.1002/chem.201604616

  日期：2016.12.5

  Morita–Baylis–Hillman (MBH) reaction was developed. By mass spectrometric back‐reaction screening of quasi‐enantiomeric MBH products, an efficient bifunctional phosphine catalyst was identified that outperforms literature‐known catalysts in the MBH reaction of methyl acrylate with aldehydes. The close match between the selectivities measured for the forward and back reaction and kinetic measurements provided

  建立了评估不对称森田-贝利斯-希尔曼（MBH）反应催化剂的有效方案。通过对映异构体MBH产物的质谱反向反应筛选，发现一种有效的双功能膦催化剂在丙烯酸甲酯与醛类的MBH反应中性能优于文献中已知的催化剂。正反反应的选择性与动力学测量之间的紧密匹配提供了有力的证据，表明醛醇缩合步骤而不是随后的质子转移是速率和对映选择性的决定因素。
• Organocatalytic Enantioselective Allylic Etherification of Morita–Baylis–Hillman Carbonates and Silanols
  作者：Hui-Li Liu、Ming-Sheng Xie、Gui-Rong Qu、Hai-Ming Guo

  DOI：10.1021/acs.joc.6b01931

  日期：2016.10.21

  The organocatalytic asymmetric allylic etherification reaction of Morita–Baylis–Hillman carbonates and silanols was reported for the first time. With modified cinchona alkaloid (DHQD)2PYR as the catalyst, a series of aromatic, heterocyclic, or aliphatic Morita–Baylis–Hillman carbonates (25 examples) worked well with triphenylsilanol, affording the corresponding products in moderate to good yields (up

  首次报道了森田-贝利斯-希尔曼碳酸盐和硅烷醇的有机催化不对称烯丙基醚化反应。以修饰的金鸡纳生物碱（DHQD）2 PYR为催化剂，一系列芳族，杂环或脂肪族Morita-Baylis-Hillman碳酸盐（25个实例）与三苯基硅烷醇效果很好，从而提供了中等至良好收率的相应产品（高达98 ％），高区域选择性（> 20：1）和良好的对映选择性（最高92％）。当使用二甲基苯基硅烷醇作为亲核试剂时，以60％的收率和87％的ee获得产物。
• α-Isocupreine, an Enantiocomplementary Catalyst of β-Isocupreidine
  作者：Yoshito Nakamoto、Fumiya Urabe、Keisuke Takahashi、Jun Ishihara、Susumi Hatakeyama

  DOI：10.1002/chem.201302665

  日期：2013.9.16

  Complementary chemistry! α‐Isocupreine (α‐ICPN) was synthesized for the first time in one step from quinine by treatment with CF3SO3H (see scheme). This compound serves as an enantiocomplementary catalyst to β‐isocupreidine (β‐ICD) in the Morita–Baylis–Hillman reaction.

  互补化学！通过CF 3 SO 3 H处理，从奎宁一步一步合成了α-异cupreine（α-ICPN）（参见方案）。在Morita-Baylis-Hillman反应中，该化合物可作为β-异cupreidine（β-ICD）的对映体互补催化剂。
• Reversal of Diastereoselectivity of Nitrile Oxide 1,3-Dipolar Cycloadditions by Mg(II). Acceleration of Cycloaddition by Microwave Irradiation
  作者：Peter Mičúch、L'ubor Fišera、Michał K Cyrański、Tadeusz M Krygowski、Ján Krajčı́k

  DOI：10.1016/s0040-4020(00)00454-3

  日期：2000.7

  1,3-Dipolar cycloadditions of mesitonitrile oxide to Baylis-Hillman adducts (beta-hydroxy-alpha-methylene esters) proceed regioselectively in good yields. Addition of Grignard reagent reverses the diastereoselectivity of the cycloaddition. Microwave irradiation strongly accelerates the reaction with only a small effect on its diastereoisomeric excess. (C) 2000 Elsevier Science Ltd. All rights reserved.