Z-methyl 3-(4-benzyloxy)phenylacrylate | 84184-51-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: Z-methyl 3-(4-benzyloxy)phenylacrylate
• 英文别名: Methyl-p-benzyloxyzinnamat；Methyl 4-benzyloxy-cinnamate；methyl 3-(4-phenylmethoxyphenyl)prop-2-enoate
• CAS: 84184-51-0；73583-43-4
• 化学式: C₁₇H₁₆O₃
• 分子量: 268.312
• InChiKey: XQOAFLYGJKNOAR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Z-methyl 3-(4-benzyloxy)phenylacrylate 在 4-二甲氨基吡啶 、 palladium on carbon 、 氢气 、 potassium carbonate 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 sodium hydroxide 作用下， 以 乙醇 、 二氯甲烷 、 乙酸乙酯 、 丙酮 为溶剂， 反应 32.0h， 生成 2-(p-benzyloxyphenylpropionoyloxy)(a)-4-(3',4'-dimethoxyphenyl)(e)-trans-quinolizidine
  参考文献：
  名称：

  Total Synthesis of (±)-Decinine via an Oxidative Biaryl Coupling with Defined Axial Chirality

  摘要：

  The total synthesis of (+/-)-decinine has been achieved. The key steps in the synthesis involved the formation of lasubine II via a gold catalyzed annulation of 1-(but-3-yn-1-yl)piperidine and the formation of the 12-membered ring of decinine (1) with complementary atropselectivity via a VOF3-mediated oxidative biaryl coupling reaction.

  DOI：

  10.1021/ol3015573
• 作为产物：
  描述：

  对羟基肉桂酸 在 氯化亚砜 、 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 24.0h， 生成 Z-methyl 3-(4-benzyloxy)phenylacrylate
  参考文献：
  名称：

  含有修饰的A环和Seco-B环作为刺猬蛋白通路抑制剂的维生素D3类似物

  摘要：

  刺猬（Hh）信号传导途径是一种发育信号传导途径，已被认为是多种人类恶性肿瘤中抗癌药物开发的靶标。几个天然和合成的维生素基于d-开环-steroids已被鉴定为与化学治疗潜在的Hh信号传导的有效抑制剂。其中包括先前表征的类似物4，其中包含维生素D3（VD3）的北部CD环/侧链区域，该区域通过酯键与芳香族A环模拟物相连。为了进一步探讨此类基于VD3的Hh途径抑制剂的结构活性关系，我们设计，合成和评估了一系列修饰酯连接基的长度，组成和立体化学方向的化合物。这些研究确定了含有胺连接基和掺入对苯酚的芳香族A环的化合物54和55，它们是对Hh途径具有增强效力的新的先导化合物（IC 50值分别为0.40和0.32μM）。

  DOI：

  10.1016/j.ejmech.2015.01.049

文献信息

• METHOD FOR PRODUCING A CROSS-COUPLING PRODUCT OF A BENZENOID DIAZONIUM SALT
  申请人：Boege Nicolas

  公开号：US20130053598A1

  公开（公告）日：2013-02-28

  The invention relates to a method for producing a cross-coupling product of a benzenoid dizonium salt according to the general formula (I), wherein the groups R 1 , R 2 , R 3 , R 4 , and R 5 represent hydrogen, halogen, an alkyl, alkenyl, aryl, alkoxy, aryloxy, nitro, cyano, hydroxy, acetyl, and/or diazo groups independently of each, and X represents BF 4 , Cl, F, SO 3 CH 3 , CO 2 CH 3 , PF 6 , ClO 2 CH 3 , or CIO 4 , comprising the following steps: (a) providing a benzenoid amide, which with the exception of the diazo function has the same substituents R 1 , R 2 , R 3 , R 4 , and R 5 as the benzenoid diazonium salt of the general formula (I), and hydrolytically cleaving the amide to form an amine or providing a corresponding amine, (b) diazotizing the amine thus obtained or provided with a nitrite, and (c) subsequently reacting the benzenoid diazonium salt with a coupling partner in the presence of a catalyst to form a cross-coupling product, wherein the coupling parter is represented by the general formula (II), R 6 , R 7 , and R 8 are the same or different and represent hydrogen, carboxyalkyl groups, carboxyaryl groups, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, wherein the groups can each contain Si, N, S, O, and or halogen atoms, or R 6 and R 7 with the double bound form an aromatic ring, which can be provided with R 8 and one to four further substituents, independently of each other, selected from the group comprising a straight-chain or branched (C 1 -C 6 ) alkyl group, a (C 3 -C 7 ) cycloalkyl group, a straight-chain or branched (C 1 -C 6 ) alkenyl group, a straight-chain or branched (C 1 -C 6 ) alkyoxy group, halogen, the hydroxy group, an amino, di(C 1 -C 6 ) alkylamino, nitro, acetyl, cyan, benzyl, 4-methoxybenzyl, 4-nitrobenzyl, phenyl, and 4-methoxyphenyl group and represents Y=H, —B(OR) 2 , —SnR 3 , —ZnR, —SiR 3 , or Mg (halogen), and wherein at least the steps (b) and (c) are performed without intermediate isolation of an intermediate product. According to said method, cross-couplings can be performed more simply and with improved yield without the hydroxyl group in aromatic reactants containing hydroxyl groups having to be provided with a protective group.

  该发明涉及一种根据通式(I)制备苯并重氮盐的交叉偶联产物的方法，其中基团R1、R2、R3、R4和R5代表氢、卤素、烷基、烯基、芳基、烷氧基、芳氧基、硝基、氰基、羟基、乙酰基和/或重氮基，X代表BF4、Cl、F、SO3CH3、CO2CH3、PF6、ClO2CH3或CIO4，包括以下步骤：(a)提供苯并酰胺，除了重氮功能外，具有通式(I)中苯并重氮盐相同的取代基R1、R2、R3、R4和R5，并水解裂解酰胺形成胺或提供相应的胺，(b)用亚硝酸盐重氮得到或提供的胺，(c)随后在催化剂存在下将苯并重氮盐与偶联配体反应形成交叉偶联产物，其中偶联配体由通式(II)表示，R6、R7和R8相同或不同，代表氢、羧基烷基、羧基芳基、烷基、芳基、烷氧基、芳氧基，其中基团可以包含Si、N、S、O和/或卤素原子，或R6和R7与双键形成芳香环，可提供R8和一个到四个进一步取代基，独立于彼此，选自包括直链或支链(C1-C6)烷基、(C3-C7)环烷基、直链或支链(C1-C6)烯基、直链或支链(C1-C6)烷氧基、卤素、羟基、氨基、二(C1-C6)烷基氨基、硝基、乙酰基、氰基、苄基、4-甲氧基苄基、4-硝基苄基、苯基和4-甲氧基苯基，表示Y=H、—B(OR)2、—SnR3、—ZnR、—SiR3或Mg(卤素)，至少步骤(b)和(c)在不中间分离中间产物的情况下执行。根据该方法，可以更简单地进行交叉偶联，并且在含有羟基的芳香反应物中无需提供保护基即可获得改进的产率。
• General synthesis of epi-series catechins and their 3-gallates: reverse polarity strategy
  作者：Ken Ohmori、Takahisa Yano、Keisuke Suzuki

  DOI：10.1039/c003464a

  日期：——

  A general synthetic route to the epi-series catechins was developed based on the reverse polarity strategy. Aromatic nucleophilic substitution reaction followed by the sulfinyl–metal exchange and cyclization enabled stereo-controlled access to various members of epi-series catechins and their 3-gallates.

  基于反极性策略，开发了一条合成表儿茶素类化合物的通用合成路线。通过芳香族亲核取代反应、亚磺酰基-金属交换及环化反应，实现了多种表儿茶素及其3-没食子酸酯的立体控制合成。
• Lewis Base Catalyzed Aerobic Oxidative Intermolecular Azide-Zwitterion Cycloaddition
  作者：Wenjun Li、Jian Wang

  DOI：10.1002/anie.201408265

  日期：2014.12.15

  discovery of a novel aerobic oxidative intermolecular azide–zwitterion reaction catalyzed by an organocatalyst is presented. It is demonstrated that the merger of the Lewis base 1,8‐diazabicyclo[5.4.0]undec‐7‐ene and electron‐deficient olefins generates reactive zwitterion intermediates, which readily participate in cycloaddition reactions with an array of azides, thus providing facile entry to fully or

  提出了一种由有机催化剂催化的新型好氧氧化性分子间叠氮化物-两性离子反应的发现。结果表明，路易斯碱的1,8-二氮杂双环[5.4.0]十一碳-7烯和缺电子的烯烃的结合会生成反应性两性离子中间体，该中间体容易参与一系列叠氮化物的环加成反应，从而提供了便利进入完全或高度取代的1,2,3-三唑骨架。该反应具有优异的底物范围，并且以高收率和优异的区域选择性获得了产物。已经证明这些产品中的一些可以转化为药学上重要的试剂。除实验结果外，还提供了详细的机械调查，包括合理化区域选择性控制起源的MS研究。
• Concise total synthesis of (±)-serotobenine
  作者：Kangjiang Liang、Ting Wu、Chengfeng Xia

  DOI：10.1039/c6ob00682e

  日期：——

  A concise total synthesis of (±)-serotobenine via a strategy inspired by the biosynthetic hypothesis for this alkaloid was accomplished. The indolofuran core was constructed by an iron-catalyzed intermolecular oxidative radical cross-coupling reaction developed by our group.

  通过该生物碱的生物合成假说启发的策略，完成了简明的（±）-serotobenine的全合成。吲哚呋喃核是通过我们小组开发的铁催化的分子间氧化自由基交叉偶联反应构建的。
• Stereocontolled Synthesis of (−)-Afzelechin: General Route to Catechin-class Polyphenols by Solving an S_N2 vs. S_N1 Problem
  作者：Ken Ohmori、Megumi Takeda、Takashi Higuchi、Tomohiro Shono、Keisuke Suzuki

  DOI：10.1246/cl.2009.934

  日期：2009.9.5

  Stereocontrolled synthesis of (−)-afzelechin was achieved via the Mitsunobu reaction, where complete stereospecificity was observed when an electron-withdrawing group was introduced to the para-position of the B-ring fragment.

  通过 Mitsunobu 反应实现了 (-)-afzelechin 的立体定向合成，当在 B 环片段的对位引入一个抽电子基团时，可观察到完全的立体特异性。