(E)-(3-phenylprop-2-enyloxy)acetaldehyde | 321903-34-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-(3-phenylprop-2-enyloxy)acetaldehyde
• 英文别名: (E)-(3-phenylprop-2-enyloxy)ethanal；2-(cinnamyloxy)acetaldehyde；2-[(E)-3-phenylprop-2-enoxy]acetaldehyde
• CAS: 321903-34-8
• 化学式: C₁₁H₁₂O₂
• 分子量: 176.215
• InChiKey: UNYMZJDYIAIFIA-QPJJXVBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 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：

  (E)-(3-phenylprop-2-enyloxy)acetaldehyde 在 咪唑 、 盐酸羟胺 、 碳酸氢钠 作用下， 以 乙醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 生成 (E)-(3-phenylprop-2-enyloxy)acetaldehyde O-tert-butyldimethylsilyloxime
  参考文献：
  名称：

  Intramolecular Cycloaddition of O-tert-Butyldimethylsilyloximes in the Presence of BF₃·OEt₂

  摘要：

  Intramolecular cycloaddition of novel 1,3-dipoles, N-boranonitrones, was examined. Treatment of O-tert-butyldimethylsilyloximes 9-12 having olefin moieties with 2 equiv of BF3 center dot OEt2 generated N-boranonitrones, which underwent intramolecular cycloaddition to afford N-nonsubstituted cycloadducts 16 (and/or 18) after extractive workup. Despite the Lewis-acidic conditions, the olefin geometry of the substrates was retained in the cycloadducts in the present cycloaddition. The electronic nature of the N-boranonitrones appeared to be electrophilic. In the case of substrate 11c, having an electron-donating methyl group at an internal position of the olefin moiety, the cycloaddition gave the bridged cycloadduct 18b. The cycloaddition proceeded at relatively low temperature, and the diastereoselectivity was high.

  DOI：

  10.1021/jo051652e
• 作为产物：
  描述：

  Methyl (E)-6-phenyl-3-oxahex-5-enoate 在 lithium aluminium tetrahydride 、 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 (E)-(3-phenylprop-2-enyloxy)acetaldehyde
  参考文献：
  名称：

  Intramolecular Cycloaddition of O-tert-Butyldimethylsilyloximes in the Presence of BF₃·OEt₂

  摘要：

  Intramolecular cycloaddition of novel 1,3-dipoles, N-boranonitrones, was examined. Treatment of O-tert-butyldimethylsilyloximes 9-12 having olefin moieties with 2 equiv of BF3 center dot OEt2 generated N-boranonitrones, which underwent intramolecular cycloaddition to afford N-nonsubstituted cycloadducts 16 (and/or 18) after extractive workup. Despite the Lewis-acidic conditions, the olefin geometry of the substrates was retained in the cycloadducts in the present cycloaddition. The electronic nature of the N-boranonitrones appeared to be electrophilic. In the case of substrate 11c, having an electron-donating methyl group at an internal position of the olefin moiety, the cycloaddition gave the bridged cycloadduct 18b. The cycloaddition proceeded at relatively low temperature, and the diastereoselectivity was high.

  DOI：

  10.1021/jo051652e

文献信息

• Tributyltin hydride-mediated radical cyclisation of aldehydes and unsaturated ketones: the synthesis of hydroxy tetrahydrofurans, chromanols and related compounds
  作者：David Bebbington、Jon Bentley、Paul A Nilsson、Andrew F Parsons

  DOI：10.1016/s0040-4039(00)01586-0

  日期：2000.11

  The tributyltin hydride-mediated cyclisation of unsaturated ethers bearing an aldehyde or α,β-unsaturated ketone group is reported. Cyclisation proceeds via addition of the tributyltin radical to the carbonyl double bond and the resultant O-stannyl ketyl can add intramolecularly to electron-rich double bonds to form hydroxy tetrahydrofurans, chromanols or related compounds.

  据报道，三丁基氢化锡介导的带有醛或α，β-不饱和酮基的不饱和醚的环化。环化反应是通过将三丁基锡自由基加到羰基双键上而进行的，所得的O-锡烷基缩酮可以分子内加至富电子双键上，形成羟基四氢呋喃，苯并二氢呋喃或相关化合物。
• Catalytic Olefin Hydroamination with Aminium Radical Cations: A Photoredox Method for Direct C–N Bond Formation
  作者：Andrew J. Musacchio、Lucas Q. Nguyen、G. Hudson Beard、Robert R. Knowles

  DOI：10.1021/ja5056774

  日期：2014.9.3

  While olefin amination with aminium radical cations is a classical method for C-N bond formation, catalytic variants that utilize simple 2° amine precursors remain largely undeveloped. Herein we report a new visible-light photoredox protocol for the intramolecular anti-Markovnikov hydroamination of aryl olefins that proceeds through catalytically generated aminium radical intermediates. Mechanistic studies

  虽然用胺自由基阳离子进行烯烃胺化是形成 CN 键的经典方法，但利用简单 2° 胺前体的催化变体在很大程度上仍未开发。在此，我们报告了一种新的可见光光氧化还原方案，用于芳基烯烃的分子内抗马尔科夫尼科夫加氢胺化，该方案通过催化生成的胺自由基中间体进行。机理研究与涉及胺氧化的过程一致，包括通过电子转移、限制周转的 CN 键形成和第二个电子转移步骤以减少以碳为中心的自由基，从而使整个过程氧化还原中性。一系列结构多样的 N-芳基杂环可以在比传统的基于胺的方案所需的条件温和得多的条件下以良好到优异的产率制备。
• Tributyltin hydride-mediated radical cyclisation of carbonyls to form functionalised oxygen and nitrogen heterocycles
  作者：Jon Bentley、Paul A. Nilsson、Andrew F. Parsons

  DOI：10.1039/b202077g

  日期：2002.6.7

  The tributyltin hydride-mediated cyclisation of unsaturated ethers and amines bearing an aldehyde or α,β-unsaturated ketone group is reported. Cyclisation proceeds via reversible addition of the tributyltin radical to the carbonyl double bond to form an intermediate O-stannyl ketyl. This nucleophilic radical can add intramolecularly to electron-rich double bonds to form substituted 5- or 6-membered

  三丁基氢化锡介导的不饱和环化反应 醚 和 胺类 轴承 醛 或α，β-不饱和 酮 组被报告。 环化前进经由可逆加成的三丁基锡的基团的羰双键形成中间体O-锡烷基缩酮。该亲核基团可以分子内加至富含电子的双键上，以形成取代的5或6元环。环化形成例如羟基四氢呋喃的效率，铬醇 或者 喹诺酮类所显示的R 1取决于受体双键的性质以及中间体O-锡烷基缩酮的稳定性。因此，首次显示出共振稳定的烯丙基或苄基的O-锡烷基酮基自由基在缓慢的自由基环化中具有特殊的应用，从而导致丁内酯或吡喃。
• Chemoselective and Diastereoselective Intramolecular (3+2) Cycloadditions of Epoxy and Aziridinyl Enolsilanes
  作者：Yueyao Chen、Jesse Ling、Angus B. Keto、Yun He、Kam‐Hung Low、Elizabeth H. Krenske、Pauline Chiu

  DOI：10.1002/anie.202116099

  日期：2022.5.16

  Epoxy and aziridinyl enolsilanes react as oxyallylic cation equivalents in diastereoselective intramolecular stepwise (3+2) cycloadditions with acyclic dienes, outcompeting the (4+3) cycloaddition pathway almost exclusively. Computations reveal the factors behind this preference. Optically-enriched trans-hydrindanone cycloadducts can be generated.

  环氧和氮丙啶烯醇硅烷在非对映选择性分子内逐步 (3+2) 环加成反应中与无环二烯反应，几乎完全胜过 (4+3) 环加成途径。计算揭示了这种偏好背后的因素。可以产生光学富集的反式-氢化茚酮环加合物。
• Ketone–Olefin Coupling of Aliphatic and Aromatic Carbonyls Catalyzed by Excited-State Acridine Radicals
  作者：Nicholas J. Venditto、Yiyang S. Liang、Roukaya K. El Mokadem、David A. Nicewicz

  DOI：10.1021/jacs.2c04822

  日期：2022.7.6

  easily reducible aromatic carbonyl compounds. Herein, we describe a mild, metal-free ketone–olefin coupling reaction using an excited-state acridine radical super reductant as a photoredox catalyst. We demonstrate both intramolecular and intermolecular ketone–olefin couplings of aliphatic and aromatic ketones and aldehydes. Mechanistic evidence is also presented supporting an “olefin first” ketone–olefin

  酮-烯烃偶联反应是形成碳-碳键的常用方法。该反应类别通常需要化学计量或超化学计量的金属还原剂，并且催化变化在应用中受到限制。光氧化还原催化为酮-烯烃偶联反应提供了一种替代方法，尽管大多数方法仅限于易于还原的芳香族羰基化合物。在这里，我们描述了一种温和的、无金属的酮-烯烃偶联反应，使用激发态吖啶自由基超级还原剂作为光氧化还原催化剂。我们展示了脂肪族和芳香族酮和醛的分子内和分子间酮-烯烃偶联。还提供了支持“烯烃优先”的机制证据酮-烯烃偶联机理。