(1E,3R)-(+)-2-methyl-1-phenylhexa-1,5-dien-3-ol

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: (1E,3R)-(+)-2-methyl-1-phenylhexa-1,5-dien-3-ol
• 英文别名: (R)-(+)-(E)-2-methyl-1-phenylhexa-1,5-dien-3-ol；(E,R)-(+)-2-methyl-1-phenylhexa-1,5-dien-3-ol；(1E,3R)-2-methyl-1-phenyl-1,5-hexadiene-3-ol；(R),(E)-2-methyl-1-phenyl-hexa-1,5-dien-3-ol；(1E,3R) 2-methyl-1-phenyl-1,5-hexadien-3-ol；(1E,3R)-2-methyl-1-phenylhexa-1,5-dien-3-ol
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: BJWFWSDUVKVFLO-OCHBPSSRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  反式-alpha-甲基肉桂醛 在 锰 、 chiral tethered bis(8-quinolinolato) chromium 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 乙腈 为溶剂， 反应 18.0h， 生成 (1E,3R)-(+)-2-methyl-1-phenylhexa-1,5-dien-3-ol
  参考文献：
  名称：

  催化对映选择性 Nozaki-Hiyama 烯丙基化反应与系留双 (8-喹啉) (TBOx) 铬配合物

  摘要：

  进一步探索了新型手性配体系链双（8-羟基喹啉）（TBOxH）的用途。其铬配合物 TBOxCr(III)Cl 在室温下有效催化各种醛的 Nozaki-Hiyama 烯丙基化反应，收率高（高达 95%）和对映选择性（ee 高达 99%）。表明本方法的范围很广，并且该方法代表了获得手性高烯丙醇的有效途径。

  DOI：

  10.1021/ja058454p

文献信息

• Lewis Base Catalyzed Enantioselective Allylation of α,β-Unsaturated Aldehydes
  作者：Aneta Kadlčíková、Irena Valterová、Lucie Ducháčková、Jana Roithová、Martin Kotora

  DOI：10.1002/chem.201001523

  日期：2010.8.16

  Being selective: The catalytic allylation of α,β‐unsaturated aldehydes with allyltrichlorosilane in the presence of chiral 3,3′‐unsymmetrically substituted bis(tetrahydroisoquinoline) N,N‐dioxides was explored. The allylation of various aldehydes proceeded under mild reaction conditions (−78 °C) with high yields and enantioselectivity (see scheme). This allylation was applied in the synthesis of (

  具有选择性：探索了在手性3,3'-不对称取代的双（四氢异喹啉）N，N-二氧化物存在下，α，β-不饱和醛与烯丙基三氯硅烷的催化烯丙基化反应。各种醛的烯丙基化反应在温和的反应条件下（-78°C）以高收率和对映选择性进行（参见方案）。该烯丙基化被用于（S）-（-）-goniothalamin的合成。
• Proline-Based <i>N</i>-Oxides as Readily Available and Modular Chiral Catalysts. Enantioselective Reactions of Allyltrichlorosilane with Aldehydes
  作者：John F. Traverse、Yu Zhao、Amir H. Hoveyda、Marc L. Snapper

  DOI：10.1021/ol050814q

  日期：2005.7.1

  as an effective catalyst for the reaction of allyltrichlorosilane with aryl and alpha,beta-unsaturated aldehydes at room temperature to afford the desired homoallylic alcohols in up to 92% ee. The chiral catalyst can be easily prepared from optically pure proline in three simple steps and 60% overall yield.

  [反应：请参见文字]。鉴定出基于脯氨酸的N-氧化物，其可作为烯丙基三氯硅烷与芳基和α，β-不饱和醛在室温下反应的有效催化剂，以提供高达92％ee的所需均烯丙基醇。可以通过三个简单的步骤由旋光纯的脯氨酸轻松制备手性催化剂，且总收率为60％。
• Synthetically amenable amide derivatives of tosylated-amino acids as organocatalysts for enantioselective allylation of aldehydes: computational rationale for enantioselectivity
  作者：Debashis Ghosh、Debashis Sahu、S. Saravanan、Sayed H. R. Abdi、Bishwajit Ganguly、Noor-ul H. Khan、Rukhsana I. Kureshy、Hari C. Bajaj

  DOI：10.1039/c3ob27513b

  日期：——

  A phenylalanine derived chiral amide is developed that serves as an effective organocatalyst for the reaction of allyltrichlorosilane with aryl, hetero-aryl and α,β-unsaturated aldehydes to afford the desired homoallylic alcohols in good yield (up to 90%) and high enantioselectivity (up to 99%). The experimental results and DFT calculations suggest that para substituted aromatic aldehydes as substrate show higher ee in the product than their ortho/meta counterparts. The 1H and 13C NMR spectra study corroborated the calculated results. The chiral organocatalyst can be easily synthesized from optically pure phenylalanine in two simple steps with 90% overall yield.

  开发了一种由苯丙氨酸衍生的手性酰胺，它作为有效的有机催化剂，用于烯丙基三氯硅烷与芳基、杂芳基和α,β-不饱和醛的反应，以良好的产率（高达90%）和高对映选择性（高达99%）得到所需的同烯丙基醇。实验结果和DFT计算表明，与邻/间位取代的芳香醛相比，对位取代的芳香醛作为底物在产物中显示出更高的对映体过量值。1H和13C NMR光谱学研究证实了计算结果。手性有机催化剂可以通过两个简单步骤从光学纯苯丙氨酸轻松合成，总产率为90%。
• Oxazoline derivatives tagged with tosylated amino acids as recyclable organocatalysts for enantioselective allylation of aldehydes
  作者：Debashis Ghosh、Arghya Sadhukhan、Nabin Ch. Maity、Sayed H. R. Abdi、Noor-ul H. Khan、Rukhsana I. Kureshy、Hari C. Bajaj

  DOI：10.1039/c3ra47424k

  日期：——

  of amino acid-based oxazoline compounds have been prepared and successfully applied to the enantioselective allylation reaction of aldehydes. The fine-tuning of the structure of the oxazolines led to (S,S)-4 as an efficient organocatalyst which gave homoallyl alcohols in good yield (up to 90%) and excellent ee (up to 99%) for a wide range of substrates including aromatic, hetero-aromatic and α,β-unsaturated

  已经制备了一系列基于氨基酸的恶唑啉化合物并将其成功地用于醛的对映选择性烯丙基化反应。恶唑啉结构的微调导致了（S，S）-4作为一种有效的有机催化剂，在很宽的范围内都能得到高收率（高达90％）和良好的ee（高达99％）的均烯丙基醇。底物包括芳族，杂芳族和α，β-不饱和醛。通过三个简单的步骤合成了手性有机催化剂，总收率达88％，并成功地回收了多达三个循环。根据实验观察结果和NMR研究，提出了该反应的可能机理。
• Axial-Chiral Biisoquinoline<i>N</i>,<i>N</i>′-Dioxides Bearing Polar Aromatic C-H Bonds as Catalysts in Sakurai-Hosomi-Denmark Allylation
  作者：Carlyn Reep、Pierpaolo Morgante、Roberto Peverati、Norito Takenaka

  DOI：10.1021/acs.orglett.8b02457

  日期：2018.9.21

  as Lewis base catalysts are reported. Lewis bases containing the 3,5-bis(trifluoromethyl)phenyl group were found to be significantly more enantioselective for a wider range of substrates than those bearing aromatic residues that are not strongly electron-deficient in the allylation of aldehydes with allyltrichlorosilane. Also, optically pure 3,3′-dibromo-1,1′-biisoquinoline N,N′-dioxide that has not

  报道了设计，合成和评价带有极性芳族CH键的路易斯-碱催化剂的轴向手性双异喹啉。发现含有3，5-双（三氟甲基）苯基的路易斯碱对于较宽范围的底物比带有醛基的电子具有更大的对映选择性，所述芳族残基在醛与烯丙基三氯硅烷的烯丙基化中不是强电子缺陷的。另外，合成了以前没有报道的光学纯的3,3'-二溴-1,1'-二异喹啉N，N'-二氧化物作为常用的催化剂前体，以促进研究。