1-methoxy-4-((1E)-penta-1,3-dien-1-yl)benzene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-methoxy-4-((1E)-penta-1,3-dien-1-yl)benzene
• 英文别名: 1-methoxy-4-[(1E)-penta-1,3-dienyl]benzene
• 化学式: C₁₂H₁₄O
• 分子量: 174.243
• InChiKey: OWXNYLMFVVNADO-DSSYRYGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-methoxy-4-((1E)-penta-1,3-dien-1-yl)benzene 在 氧气 、 tetraphenylporphyrin 作用下， 以 苯 为溶剂， 反应 15.0h， 以83%的产率得到(3S,6S)-3-(4-Methoxy-phenyl)-6-methyl-3,6-dihydro-[1,2]dioxine
  参考文献：
  名称：

  Tetraphenylporphine-Sensitized Photooxygenation of (E,E)- and (E,Z)-1-Aryl-1,3-pentadienes Generating cis-Endoperoxides

  摘要：

  Photooxygenation of either (E,E)- or (E,Z)-1-aryl-1,3-pentadienes (la-c) sensitized with tetraphenylporphine (TPP) in benzene gave almost all cis-endoperoxides (2a-c) (cis-3-aryl-6-methyl-1,2-dioxacyclohex-4-enes) in good yields. A time course study of photooxygenation of(E,Z)-rich dienes measured by IH NMR showed that singlet oxygen added exclusively to (E,E)-dienes converted from (E,Z)-dienes by photoinduced isomerization, and both rates increased when electron-donating groups were attached to the aryl group. A concerted [4 + 2] cycloaddition mechanism is suggested by the exclusive formation of cis-endoperoxides from (E,E)-dienes, despite the small energy difference between cis- and trans-endoperoxides calculated by ab initio methods. Some experiments were made to explore the observed isomerization.

  DOI：

  10.1021/jo981506r
• 作为产物：
  描述：

  4-甲氧基肉桂醛 在 吡啶 、 四(三苯基膦)钯 作用下， 以 二氯甲烷 、 水 、 1,2-二氯乙烷 为溶剂， 反应 48.0h， 生成 1-methoxy-4-((1E)-penta-1,3-dien-1-yl)benzene
  参考文献：
  名称：

  钯催化多烯酸的化学选择性原羧化

  摘要：

  提出了首先钯催化的多烯酸的化学选择性原脱羧以良好的收率得到所需的多烯的条件。反应在温和的条件下使用Pd（0）或Pd（II）催化剂进行，并能耐受各种芳基和脂肪族取代。反应的独特方面包括需要膦，水和与羧酸相邻的多烯。

  DOI：

  10.1021/acs.orglett.8b03016

文献信息

• Palladium-Catalyzed Regio- and Enantioselective Hydrosulfonylation of 1,3-Dienes with Sulfinic Acids: Scope, Mechanism, and Origin of Selectivity
  作者：Qinglong Zhang、Dongfang Dong、Weiwei Zi

  DOI：10.1021/jacs.0c05976

  日期：2020.9.16

  widespread use in pharmaceutical chemistry. In particular, chiral allylic sulfones have drawn particular interest because of their synthetic utility. However, enantioselective synthesis of 1,3-disubstituted unsymmetrical chiral allylic sulfones remains a challenge. In this article, we report a protocol for (R)-DTBM-Segphos/Pd-catalyzed regio- and enantioselective hydrosulfonylation of 1,3-dienes with sulfinic

  由于其在药物化学中的广泛应用，手性砜是有机合成中的重要结构基序。特别是，手性烯丙基砜因其合成效用而引起了特别的兴趣。然而，1,3-二取代的不对称手性烯丙基砜的对映选择性合成仍然是一个挑战。在本文中，我们报告了 (R)-DTBM-Segphos/Pd 催化的 1,3-二烯与亚磺酸的区域选择性和对映选择性氢磺酰化的方案，该方案提供了原子和步骤经济的 1,3-二取代手性烯丙基砜。反应条件温和，底物范围广。结合实验和计算研究表明，反应是由配体到配体的氢转移引发的，然后是通过六元过渡态的 CS 键还原消除。发现底物的烯烃 CH 与 (R)-DTBM-Segphos 的叔丁基之间的空间排斥是对映控制的关键因素。
• Brønsted acid and Pd–PHOX dual-catalysed enantioselective addition of activated C-pronucleophiles to internal dienes
  作者：Sangjune Park、Nathan J. Adamson、Steven J. Malcolmson

  DOI：10.1039/c9sc00633h

  日期：——

  We describe the development of Pd–PHOX-catalysed enantioselective couplings of internal dienes with malononitrile and other activated C-pronucleophiles. Reactions are dramatically accelerated by the addition of Et3N·HBArF4 as a Brønsted acid co-catalyst, enabling a suite of products bearing a variety of alkyl substituents at the stereogenic carbon to be prepared. A series of mechanism-oriented experiments

  我们描述了 Pd-PHOX 催化的内部二烯与丙二腈和其他活化的 C-亲核试剂的对映选择性偶联的发展。添加 Et 3 N·HBAr F 4作为布朗斯台德酸助催化剂可显着加速反应，从而能够制备出一系列在立体碳上带有各种烷基取代基的产物。一系列以机理为导向的实验揭示了催化循环的关键方面以及非配位BAr F 4反离子的重要性，不仅促进了内部二烯的反应，而且还促进了先前不反应的亲核试剂向末端二烯的添加。
• Development and Mechanistic Investigations of Enantioselective Pd-Catalyzed Intermolecular Hydroaminations of Internal Dienes
  作者：Sangjune Park、Steven J. Malcolmson

  DOI：10.1021/acscatal.8b01914

  日期：2018.9.7

  generate allylic amines with myriad α-alkyl groups in up to 78% yield, >98:2 rr, and 98.5:1.5 er. A number of experiments, including deuterium labeling and transamination studies, shed light on mechanistic details of the reaction, such as the reversibility of individual steps of the proposed catalytic cycle and of the reaction as a whole.

  我们报告了具有挑战性的1，4-二取代的无环二烯的高对映体和区域选择性Pd催化的分子间氢化反应的发展。几个芳基/烷基二取代的二烯和一个空间分化的烷基/烷基二取代的二烯与各种仲脂肪族胺，二氢吲哚和伯苯胺进行偶合，生成具有无数α-烷基的烯丙基胺，收率高达78％，> 98：2 rr和98.5：1.5 er。包括氘标记和氨基转移研究在内的许多实验揭示了反应的机理细节，例如拟议的催化循环各个步骤的可逆性以及整个反应的可逆性。
• Palladium-Catalyzed Chemoselective Protodecarboxylation of Polyenoic Acids
  作者：Mohammed H. Al-Huniti、Mark A. Perez、Matthew K. Garr、Mitchell P. Croatt

  DOI：10.1021/acs.orglett.8b03016

  日期：2018.12.7

  Conditions for the first palladium-catalyzed chemoselective protodecarboxylation of polyenoic acids to give the desired polyenes in good yields are presented. The reactions proceed under mild conditions using either a Pd(0) or Pd(II) catalyst and tolerate a variety of aryl and aliphatic substitutions. Unique aspects of the reaction include the requirement of phosphines, water, and a polyene adjacent

  提出了首先钯催化的多烯酸的化学选择性原脱羧以良好的收率得到所需的多烯的条件。反应在温和的条件下使用Pd（0）或Pd（II）催化剂进行，并能耐受各种芳基和脂肪族取代。反应的独特方面包括需要膦，水和与羧酸相邻的多烯。
• Tetraphenylporphine-Sensitized Photooxygenation of (<i>E,E</i>)- and (<i>E,Z</i>)-1-Aryl-1,3-pentadienes Generating <i>cis</i>-Endoperoxides
  作者：Jiro Motoyoshiya、Yasuyuki Okuda、Ichiro Matsuoka、Sadao Hayashi、Yutaka Takaguchi、Hiromu Aoyama

  DOI：10.1021/jo981506r

  日期：1999.1.1

  Photooxygenation of either (E,E)- or (E,Z)-1-aryl-1,3-pentadienes (la-c) sensitized with tetraphenylporphine (TPP) in benzene gave almost all cis-endoperoxides (2a-c) (cis-3-aryl-6-methyl-1,2-dioxacyclohex-4-enes) in good yields. A time course study of photooxygenation of(E,Z)-rich dienes measured by IH NMR showed that singlet oxygen added exclusively to (E,E)-dienes converted from (E,Z)-dienes by photoinduced isomerization, and both rates increased when electron-donating groups were attached to the aryl group. A concerted [4 + 2] cycloaddition mechanism is suggested by the exclusive formation of cis-endoperoxides from (E,E)-dienes, despite the small energy difference between cis- and trans-endoperoxides calculated by ab initio methods. Some experiments were made to explore the observed isomerization.