3-(allyloxy)-2-hydroxypropyl benzoate | 73097-87-7

• 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: 3-(allyloxy)-2-hydroxypropyl benzoate
• 英文别名: 2-hydroxy-3-allyloxypropyl benzoate；3-(Allyloxy)-2-hydroxypropyl benzoate；(2-hydroxy-3-prop-2-enoxypropyl) benzoate
• CAS: 73097-87-7
• 化学式: C₁₃H₁₆O₄
• 分子量: 236.268
• InChiKey: LWTFFJGXHDQLFL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-(allyloxy)-2-hydroxypropyl benzoate 在 辛醇 、 Muchor miehei lipase 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 、 甲基叔丁基醚 、 异丙醚 为溶剂， 反应 48.0h， 生成 1-acetoxy-3-allyloxypropan-2-one
  参考文献：
  名称：

  Enzymatic synthesis of both enantiomeric forms of 3-allyloxy-propane-1,2-diol

  摘要：

  The stereoselective synthesis of (S)- and (R)-3-allyloxy-propane-1,2-diol has been accomplished in four steps from (RS)-3-allyloxy-propane-1,2-diol. Only one intermediate, namely 1-benzoyloxy-3-allyloxy-2-propanone has been prepared by a chemical reaction, that is, pyridinium chlorochromate oxidation of 1-benzoyloxy-3-allyloxypropan-2-ol. All of the remaining reactions (regioselective acylations, asymmetric bioreduction of prochiral ketones, and enzymatic alcoholysis) have been carried out in the presence of biocatalysts. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.03.008
• 作为产物：
  描述：

  甘油烯丙基醚 、 苯甲酸酐 在 苯酸四丁基铵 作用下， 以 乙腈 为溶剂， 以81%的产率得到3-(allyloxy)-2-hydroxypropyl benzoate
  参考文献：
  名称：

  A green and convenient method for regioselective mono and multiple benzoylation of diols and polyols

  摘要：

  An efficient method for regioselective benzoylation of diols and polyols was developed. The benzoylation is catalyzed by only 0.2 equiv of benzoate anion in acetonitrile with the addition of a stoichiometric amount of benzoic anhydride under very mild condition, leading to high yields. Compared with all other methods, this method shows particular advantage in regioselective multiple benzoylation of polyols, and in avoiding the use of any metal-based catalysts and any amine bases, which is more environment friendly. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.12.074

文献信息

• Regioselective Benzoylation of Diols and Carbohydrates by Catalytic Amounts of Organobase
  作者：Yuchao Lu、Chenxi Hou、Jingli Ren、Xiaoting Xin、Hengfu Xu、Yuxin Pei、Hai Dong、Zhichao Pei

  DOI：10.3390/molecules21050641

  日期：——

  A novel metal-free organobase-catalyzed regioselective benzoylation of diols and carbohydrates has been developed. Treatment of diol and carbohydrate substrates with 1.1 equiv. of 1-benzoylimidazole and 0.2 equiv. of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in MeCN under mild conditions resulted in highly regioselective benzoylation for the primary hydroxyl group. Importantly, compared to most commonly

  已经开发出一种新型的无金属有机碱催化的二醇和碳水化合物的区域选择性苯甲酰化。用 1.1 当量处理二醇和碳水化合物底物。1-苯甲酰咪唑和 0.2 当量。1,8-二氮杂双环[5.4.0] undec-7-ene (DBU) 在温和条件下在 MeCN 中的反应导致伯羟基的高度区域选择性苯甲酰化。重要的是，与最常用的伯羟基保护基团相比，苯甲酰基保护基团提供了一种新的保护策略。
• Fast Addition of s‐Block Organometallic Reagents to CO ₂ ‐Derived Cyclic Carbonates at Room Temperature, Under Air, and in 2‐Methyltetrahydrofuran
  作者：David Elorriaga、Felipe Cruz‐Martínez、María Jesús Rodríguez‐Álvarez、Agustín Lara‐Sánchez、José Antonio Castro‐Osma、Joaquín García‐Álvarez

  DOI：10.1002/cssc.202100262

  日期：2021.5.6

  straightforward synthesis of: highly substituted tertiary alcohols, β‐hydroxy esters, or symmetric ketones, working always under air and at room temperature. Finally, an unprecedented one‐pot/two‐step hybrid protocol is developed through combination of an Al‐catalyzed cycloaddition of CO2 and propylene oxide with the concomitant fast addition of RLi reagents to the in situ and transiently formed cyclic carbonate

  在2-甲基四氢呋喃中作为绿色反应介质或在没有外部挥发性有机溶剂的情况下，已在室温下研究了将高极性有机金属试剂（RMgX / RLi）快速添加到环状碳酸酯（衍生自CO 2作为可持续的C1合成子）中的情况。温度，以及空气/水分的存在。这些高反应性的主族有机金属化合物通常禁止这些反应条件。极性有机金属烷基化或芳基化试剂的正确化学计量和性质可直接合成：高取代度叔醇，β羟基酯或对称酮始终在空气和室温下工作。最后，通过将Al 2催化的CO 2和环氧丙烷的环加成反应以及随之而来的RLi试剂快速快速添加到原位和短暂形成的环状碳酸酯中，开发出了前所未有的单罐/两步混合方案。将CO 2转化为所需的高度取代的叔醇，而无需分离或纯化任何反应中间体。
• Regioselective Sulfonylation/Acylation of Carbohydrates Catalyzed by FeCl₃ Combined with Benzoyltrifluoroacetone and Its Mechanism Study
  作者：Jian Lv、Jia-Jia Zhu、Yu Liu、Hai Dong

  DOI：10.1021/acs.joc.9b03128

  日期：2020.3.6

  A catalytic amount of FeCl3 combined with benzoyl trifluoroacetone (Hbtfa) (FeCl3/Hbtfa = 1/2) was used to catalyze sulfonylation/acylation of diols and polyols using diisopropylethylamine (DIPEA) or potassium carbonate (K2CO3) as a base. The catalytic system exhibited high catalytic activity, leading to excellent isolated yields of sulfonylation/acylation products with high regioselectivities. Mechanism

  使用二异丙基乙胺（DIPEA）或碳酸钾（K2CO3）作为碱，将催化量的FeCl3与苯甲酰基三氟丙酮（Hbtfa）（FeCl3 / Hbtfa = 1/2）结合用于催化二醇和多元醇的磺酰化/酰化。该催化体系表现出高催化活性，导致具有高区域选择性的磺酰化/酰化产物的优异分离产率。机理研究表明，FeCl3最初在碱性条件下于室温下于溶剂乙腈中以两倍的Hbtfa量形成[Fe（btfa）3]（btfa =苯甲酰基三氟丙酮酸酯）。然后，在碱的存在下，Fe（btfa）3和底物的两个羟基形成五元或六元环中间体。环状中间体和磺酰化试剂之间的随后反应导致底物的选择性磺酰化。所有关键中间体均在高分辨率质谱分析中捕获，因此首次证明了这种机理。
• An inexpensive catalyst, Fe(acac)₃, for regio/site-selective acylation of diols and carbohydrates containing a 1,2-<i>cis</i>-diol
  作者：Jian Lv、Jian-Tao Ge、Tao Luo、Hai Dong

  DOI：10.1039/c8gc00428e

  日期：——

  This work describes the [Fe(acac)3] (acac = acetylacetonate)-catalyzed, regio/site-selective acylation of 1,2- and 1,3-diols and glycosides containing a cis-vicinal diol. The iron(III) catalysts initially formed cyclic dioxolane-type intermediates with substrates between the iron(III) species and vicinal diols, and the efficient and selective acylation of one hydroxyl group was subsequently achieved

  这项工作描述了[Fe（acac）3 ]（acac =乙酰丙酮酸酯）催化的1,2-和1,3-二醇和含有顺式邻位二醇的糖苷的区域/位点选择性酰化。铁（III）催化剂最初形成环状二氧戊环型中间体，底物在铁（III）物种与邻位二醇之间，随后通过在二异丙基乙胺（DIPEA）存在下添加酰化试剂，实现一个羟基的有效和选择性酰化）在温和的条件下。该反应通常产生高选择性和高分离产率，并具有与二丁基氧化锡介导的方案相同的保护模式。
• Stannous chloride as a low toxicity and extremely cheap catalyst for regio-/site-selective acylation with unusually broad substrate scope
  作者：Jian Lv、Jian-Cheng Yu、Guang-Jing Feng、Tao Luo、Hai Dong

  DOI：10.1039/d0gc02739a

  日期：——

  containing cis-vicinal diol, the substrate scope also includes glycosides without cis-vicinal diol. For such a substrate scope, usually, only methods using stoichiometric amounts of organotin reagents can lead to the same protection pattern with high selectivities and highly isolated yields (84–97% in most cases). Therefore, SnCl2, as a low toxicity and extremely cheap reagent, should be the best catalyst

  这项工作报告了氯化亚锡（SnCl 2）催化的区域/位点选择性酰化反应，其底物范围异常广泛。除了含有顺式-邻位二醇的1,2-和1,3-二醇和糖苷外，底物范围还包括不含顺式-邻位二醇的糖苷。对于这种底物范围，通常，只有使用化学计量的有机锡试剂的方法才能以高选择性和高分离产率（大多数情况下为84–97％）产生相同的保护模式。因此，与以前报道的任何试剂相比，SnCl 2作为一种低毒且极其便宜的试剂，应该是区域/位点选择性酰化反应的最佳催化剂。