(1E,3S)-(-)-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,3S)-(-)-2-methyl-1-phenylhexa-1,5-dien-3-ol
• 英文别名: (S)-(-)-(E)-2-methyl-1-phenylhexa-1,5-dien-3-ol；(E,S)-(-)-2-methyl-1-phenylhexa-1,5-dien-3-ol；(1E,3S)-2-methyl-1-phenyl-1,5-hexadiene-3-ol；(1E,3R)-2-methyl-1-phenylhexa-1,5-dien-3-ol；(E)-2-methyl-1-phenyl-hexa-1,5-dien-3-ol；(1E,3S)-2-methyl-1-phenylhexa-1,5-dien-3-ol
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: BJWFWSDUVKVFLO-NHAQELONSA-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：

  3-氯丙烯 、 反式-alpha-甲基肉桂醛 在 chromium chloride 、 锰 、 (1R,8S,9R,1'R,8'S,9'R)-2-[8'-(1-hydroxy-1-methylethyl)-10,10,10',10'-tetramethyl-[5,5']bi[6-azatricyclo[7.1.1.0(2,7)]undecyl]-2(7),3,5,2',4',6'-hexaen-8-yl]propan-2-ol 、 三乙胺 、 三甲基氯硅烷 、 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 25.25h， 以90%的产率得到(1E,3S)-(-)-2-methyl-1-phenylhexa-1,5-dien-3-ol
  参考文献：
  名称：

  C 2-对称联吡啶二醇作为有望在对崎-Hiyama烯丙基化中的对映体选择性催化剂

  摘要：

  合成了几种新的手性联吡啶二醇配体，这些配体促进了铬催化烯丙基卤化物在不超过99％ee的条件下对醛的对映选择性加成。在氯化铬（III）和烯丙基氯的存在下，使用配体4和4a进行的铬催化醛的烯丙基化提供了最高的对映选择性。

  DOI：

  10.1002/adsc.201100023

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%。
• Enantioselective Allylation of Aldehydes Catalyzed by Diastereoisomeric Bis(tetrahydroisoquinoline) N,N′-Dioxides
  作者：Klára Vlašaná、Radim Hrdina、Irena Valterová、Martin Kotora

  DOI：10.1002/ejoc.201001219

  日期：2010.12

  enantioselectivity up to 96 %. On the other hand, the allylation of aromatic aldehydes in the presence of the (R,R ax ,R) catalyst proceeded only in MeCN (up to 67 % ee), and the level of asymmetric induction was strongly influenced by the presence of electron-donating and -accepting groups in the aldehyde. The allylation of α,β-unsaturated aldehydes proceeded only in dichloromethane (enantioselectivity

  在两种非对映异构体 (R,R ax ,R)- 和 (R,S ax ,R)-bis-1,1'-[5,6,7,研究了 8-四氢-3-(四氢呋喃-2-基)异喹啉]N,N'-二氧化物。反应过程受所选溶剂的影响很大。(R,S ax ,R) 催化剂有效地促进了 THF 中的反应，对映选择性高达 96%。另一方面，在 (R,R ax ,R) 催化剂存在下芳香醛的烯丙基化仅在 MeCN（高达 67 % ee）中进行，并且不对称诱导的水平受到电子存在的强烈影响。醛中的供体和受体基团。α,β-不饱和醛的烯丙基化仅在二氯甲烷中进行（对映选择性高达 68%）。
• Tetrahydroisoquinoline-Based N-Oxides as Chiral Organocatalysts for the Asymmetric Allylation of Aldehydes
  作者：Tricia Naicker、Per I. Arvidsson、Hendrik G. Kruger、Glenn E. M. Maguire、Thavendran Govender

  DOI：10.1002/ejoc.201100923

  日期：2011.12

  The short synthesis of a series of novel chiral N-oxideorganocatalysts and their evaluation in the asymmetric allylation reaction of aromatic and α-β-unsaturated aldehydes with allyltrichlorosilane is reported. These readily modifiable organocatalysts are the first of their kind based on the tetrahydroisoquinoline framework. The chiral homoallyl products were obtained with good chemical efficiency

  报道了一系列新型手性 N-氧化物有机催化剂的短合成及其在芳烃和 α-β-不饱和醛与烯丙基三氯硅烷的不对称烯丙基化反应中的评价。这些易于改性的有机催化剂是基于四氢异喹啉骨架的同类有机催化剂中的第一个。在温和的反应条件 (23 °C) 下，以良好的化学效率（高达 93% 的产率）和高对映选择性（高达 91% ee）获得了手性高烯丙基产物。