methyl 2-(hydroxy(4-(trifluoromethyl)phenyl)methyl)acrylate | 353506-66-8

• 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: methyl 2-(hydroxy(4-(trifluoromethyl)phenyl)methyl)acrylate
• 英文别名: methyl 2-[hydroxy-[4-(trifluoromethyl)phenyl]methyl]prop-2-enoate
• CAS: 353506-66-8
• 化学式: C₁₂H₁₁F₃O₃
• mdl: MFCD11523089
• 分子量: 260.213
• InChiKey: MAYIKXYPBWXHSD-UHFFFAOYSA-N

物化性质

• 沸点：
  333.6±42.0 °C(Predicted)
• 密度：
  1.288±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2-(hydroxy(4-(trifluoromethyl)phenyl)methyl)acrylate 在 indium 、 氢溴酸 、 溶剂黄146 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 4.0h， 生成 cis-methyl 4-hydroxy-2-methylene-4-phenyl-3-(4-(trifluoromethyl)phenyl)butanoate
  参考文献：
  名称：

  Syntheses of β- and γ-fluorophenyl cis- and trans-α-methylene-γ-butyrolactones

  摘要：

  Preparation of a series of cis-gamma-fluorophenyl-beta-phenyl-alpha-methylene-gamma-butyrolactones is reported via 'allylboration' of fluorobenzaldehydes with (E)-methyl 3-phenyl-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)acrylate. The corresponding trans-gamma-fluorophenyl lactones were prepared either (i) via 'allylboration' using the (Z)-reagents or (ii) via an indium triflate-mediated isomerization of the cis-products. The difficulty in isomerizing difluorinated cis-products confirms the probable intermediacy of carbocations. Finally, the synthesis of cis-beta-fluorophenyl-gamma-phenyl-alpha-methylene-gamma-butyrolactones was achieved via an indium-catalyzed allylation-lactonization of aldehydes with (Z)-2-(bromomethyl)-3-(fluorophenyl)acrylates. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.07.106
• 作为产物：
  描述：

  4-(三氟甲基)苄醇 、 丙烯酸甲酯（MA） 在 硫酰氟 、 potassium carbonate 、 三乙烯二胺 作用下， 以 二甲基亚砜 为溶剂， 反应 48.0h， 以80%的产率得到methyl 2-(hydroxy(4-(trifluoromethyl)phenyl)methyl)acrylate
  参考文献：
  名称：

  SO2F2 介导伯醇的 C(sp3)-H 与缺电子烯烃的 C(sp2)-H 的级联脱氢 Morita-Baylis-Hillman 反应，用于组装烯丙醇†

  摘要：

  开发了伯醇的 C(sp 3 )-H 与缺电子烯烃的 C(sp 2 )-H 的级联脱氢 Morita-Baylis-Hillman 反应，以形成由 SO 2 F 2介导的烯丙醇。该方法为制备烯丙醇部分提供了一种温和的方法，无需过渡金属。

  DOI：

  10.1039/c9ra05346h

文献信息

• Latent Nucleophiles in Lewis Base Catalyzed Enantioselective <i>N</i> ‐Allylations of N‐Heterocycles
  作者：You Zi、Markus Lange、Constanze Schultz、Ivan Vilotijevic

  DOI：10.1002/anie.201903392

  日期：2019.7.29

  Latent nucleophiles are compounds that are themselves not nucleophilic but can produce a strong nucleophile when activated. Such nucleophiles can expand the scope of Lewis base catalyzed reactions. As a proof of concept, we report that N‐silyl pyrroles, indoles, and carbazoles serve as latent N‐centered nucleophiles in substitution reactions of allylic fluorides catalyzed by Lewis bases. The reactions

  潜在亲核试剂是本身不是亲核试剂，但在激活后会产生强亲核试剂的化合物。这样的亲核试剂可以扩大路易斯碱催化反应的范围。作为概念的证明，我们报道了在路易斯碱催化的烯丙基氟化物的取代反应中，N硅烷基吡咯，吲哚和咔唑可作为潜在的N中心亲核试剂。当使用手性金鸡纳生物碱催化剂时，两个反应伙伴的反应范围广，具有出色的区域选择性，并能产生对映体富集的N-烯丙基吡咯，吲哚和咔唑。
• Star-like polyionic heterogeneous nanocatalyst as a highly active catalyst for promotion of Baylis–Hillman reaction in [bmim]Cl
  作者：Hassan Valizadeh、Ashkan Shomali、Saeideh Noorshargh

  DOI：10.1007/s13738-015-0694-9

  日期：2015.12

  The use of star-like polyionic Lewis base heterogeneous nanocatalyst for the Baylis–Hillman reaction of benzyl- and methylacrylates with aryl aldehydes has been investigated. The corresponding Baylis–Hillman adducts are obtained in good to high yields in one-pot procedure at room temperature in 5.5–8 h. The catalyst can be easily recovered with excellent purity by filtration and can be reused directly without any change in its catalytic activity.

  研究了一种用于Baylis-Hillman反应中苄基和甲基丙烯酸酯与芳香醛反应的类似星形多离子配体异质纳米催化剂。在室温下一锅法操作5.5至8小时，相应的Baylis-Hillman加成产物以良好至高产率获得。该催化剂可通过过滤轻松回收，并保持优异的纯度，直接重复使用而不损失其催化活性。
• Regioselective dehydroxytrifluoromethylthiolation of allylic and propargylic alcohols with AgSCF3
  作者：Yin-Li Liu、Xiu-Hua Xu、Feng-Ling Qing

  DOI：10.1016/j.tetlet.2019.02.045

  日期：2019.4

  reaction of easily available Morita–Baylis–Hillman (MBH) alcohols with AgSCF3 in the presence of n-Bu4NI and KI affords primary allylic SCF3 products in high yields and excellent regioselectivities. This regioselective dehydroxytrifluoromethylthiolation protocol could also be extended to propargylic alcohols for the preparation of the primary propargylic SCF3 products.

  容易获得森田-的Baylis-希尔曼（MBH）醇与AgSCF反应3在存在Ñ -Bu 4 NI和KI得到伯烯丙基SCF 3种产品在高收率和优异的区域选择性。该区域选择性脱羟基三氟甲基硫醇化方案也可以扩展至炔丙醇，以制备初级炔丙基SCF 3产物。
• Enantioselective Trichloromethylation of MBH‐Fluorides with Chloroform Based on Silicon‐assisted C−F Activation and Carbanion Exchange Induced by a Ruppert–Prakash Reagent
  作者：Takayuki Nishimine、Hiromi Taira、Etsuko Tokunaga、Motoo Shiro、Norio Shibata

  DOI：10.1002/anie.201508574

  日期：2016.1.4

  Enantioselective trichloromethylation of Morita–Baylis–Hillman (MBH)‐type allylic fluorides with chloroform (HCCl3) under organocatalysis was achieved with high to excellent enantioselectivities. Silicon‐assisted C−F bond activation by a Ruppert–Prakash reagent and direct activation of HCCl3 by a carbanion exchange process with trifluoromethyl (CF3) carbanion generated in situ from the Ruppert‐Prakash

  在有机催化下，Morita–Baylis–Hillman（MBH）型烯丙基氟化物与氯仿（HCCl 3）的对映选择性三氯甲基化具有很高的至优异的对映选择性。通过Ruppert-Prakash试剂进行硅辅助的C-F键活化，以及通过用Ruppert-Prakash试剂原位生成的三氟甲基（CF 3）碳负离子通过碳负离子交换过程直接激活HCCl 3，实现了立体异构烯丙基上的直接不对称三氯甲基化在非常温和的条件下，无需过渡金属催化的任何帮助。HCCl 3的预活化不需要。该方法已扩展为直接对映体引入其他CH化合物，例如炔烃，芳烃，茚和FBSM，而无需在无金属系统下进行任何预活化。
• Dehydrative Cross-Coupling of Allylic Alcohols with Alkynes
  作者：Peizhong Xie、Zuolian Sun、Shuangshuang Li、Lei Zhang、Xinying Cai、Weishan Fu、Xiaobo Yang、Yanan Liu、Xiangyang Wo、Teck-Peng Loh

  DOI：10.1021/acs.orglett.0c00108

  日期：2020.2.21

  the directly dehydrative cross-coupling of allylic alcohols with terminal alkynes was developed. This calcium salt cocatalyst facilitates the oxidative addition of the palladium catalyst (1 mol %) to the C-OH bond. Then, the in situ-generated hydroxide ion deprotonates the terminal alkynes to promote the formation of the allylalkynylpalladium intermediate, liberating water as the only byproduct. This

  开发了一种高效的Pd / Ca催化体系，用于烯丙基醇与末端炔烃的直接脱水交叉偶联。该钙盐助催化剂促进了钯催化剂（1mol％）向C-OH键的氧化加成。然后，原位产生的氢氧根离子使末端炔烃去质子化，从而促进烯丙基炔基钯中间体的形成，释放出水作为唯一的副产物。密度泛函理论计算也支持这种提出的机制。由便宜的起始原料以10g规模制备抗癌剂。