5-methylene-2-phenyl-[1,3]dioxolane | 3290-74-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: 5-methylene-2-phenyl-[1,3]dioxolane
• 英文别名: 5-methylene-2-phenyl-1,3-dioxane；5-methylene-2-phenyl-[1,3]dioxane；5-Methylidene-2-phenyl-1,3-dioxane
• CAS: 3290-74-2
• 化学式: C₁₁H₁₂O₂
• 分子量: 176.215
• InChiKey: MHBNDNQNZMIHCQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2934999090

反应信息

• 作为反应物：
  描述：

  5-methylene-2-phenyl-[1,3]dioxolane 在 二异丁基氢化铝 作用下， 生成 2-(苄氧基甲基)丙-2-烯-1-醇
  参考文献：
  名称：

  Synthesis of a Functionalized Allylic Phosphine Oxide

  摘要：

  A functionalized allylic phosphine oxide has been prepared by regioselective bromination of 2-(methyldiphenylphosphinoyl)-1-propene followed by nucleophilic substitution with acetate. Hydrolysis and protection yielded the target compound.

  DOI：

  10.1080/00397919708005007
• 作为产物：
  描述：

  2-亚甲基-1,3-丙二醇 、 苯甲醛 在 氢气 作用下， 生成 5-methylene-2-phenyl-[1,3]dioxolane
  参考文献：
  名称：

  合成抗癌活性醚脂质的氟化类似物。

  摘要：

  外消旋的2'-（三甲基铵）乙基-3-十六烷基氧基-2-氟-2-（甲氧基甲基）丙-1-基磷酸酯（6）的合成，用3实现了抗癌活性醚脂质5的氟化类似物。从2-亚甲基-1,3-丙二醇（7）开始的九步合成中总产率为5％，主要步骤为溴氟化。醚脂质6的前体8的两种对映异构体都是通过脂肪酶催化的二乙酸酯17的脱对称化而合成的，或者是通过水解（83％ee）或通过脂肪酶催化的二醇22的乙酰化（82％ee）来合成的。在甲基胆碱诱导的小鼠纤维肉瘤的体内模型中发现了6的抗肿瘤活性。

  DOI：

  10.1021/jo0016172

文献信息

• Photodriven Transfer Hydrogenation of Olefins
  作者：Dasheng Leow、Ying-Ho Chen、Tzu-Hang Hung、Ying Su、Yi-Zhen Lin

  DOI：10.1002/ejoc.201403021

  日期：2014.11

  An improved practical method for the photodriven diimide reduction of olefins was investigated. This catalyst-free procedure proceeds at ambient temperature, utilizes air as oxidant and a lower hydrazine loading, and produces inert nitrogen gas as the sole byproduct. Several functional groups were tolerated, and in some cases, the reaction was chemoselective. Challenging substrates such as cinnamate

  研究了一种改进的用于烯烃的光驱动二酰亚胺还原的实用方法。这种无催化剂的过程在环境温度下进行，利用空气作为氧化剂和较低的肼负载，并产生惰性氮气作为唯一的副产品。几个官能团是可以容忍的，在某些情况下，反应是化学选择性的。具有挑战性的底物如肉桂酸酯衍生物和反式二苯乙烯以极好的产率减少。从家用紧凑型荧光灯泡发出的少量 UVA 射线被提议用于使二酰亚胺的顺式/反式异构化并促进氢从二酰亚胺中的损失。
• Addition of electrophiles to unsymmetric alkenes. Effects of β oxygen substituents on the stereo- and regio-chemistry of positive halogen addition
  作者：(The late) John Hudec、John W. Liebeschuetz

  DOI：10.1039/a801001c

  日期：——

  The stereo- and regio-chemistry of two step additions of positive halogen electrophiles to 5-methylene-2-phenyl-1,3-dioxane, 1-tert-butyl-4-methylenecyclohexane and 3-methoxy-2-(methoxymethyl)prop-1-ene have been determined. The direction of initial electrophile attack is in line with the frontier orbital and electrostatic considerations described by us previously. The regiochemistry of addition is

  阳性卤素亲电体的两步相加立体和区域-化学以5-亚甲基-2-苯基-1,3-二恶烷，1-叔已经确定了丁基-4-亚甲基环己烷和3-甲氧基-2-（甲氧基甲基）丙-1-烯。初始亲电分子攻击的方向与我们先前描述的前沿轨道和静电考虑相一致。添加的区域化学作用受到中间表卤离子与βC–X键之间的超共轭作用的强烈影响。当βC–X键与上hal离子具有固定的平面关系，且X比氢更具负电性时，强烈地促进了Markownikoff的抗加成作用，当存在两个这样的βC–X键时，抗Markownikoff加成作用会被排斥。如果βC–X键可以自由旋转远离平面，那么βC–H键将采用超共轭所需的几何构型，并且Markownikoff区域化学将受到青睐。结果与从头开始进行理论计算，并且可以使用简单的静电模型进行合理化。
• Origin of stereofacial selectivity in electrophilic additions to methylenecyclohexanes and methylenedioxanes. A theoretical and experimental study
  作者：John Hudec、Jerry Huke、John W. Liebeschuetz

  DOI：10.1039/a800999f

  日期：——

  Addition reaction studies and ab initio calculations on methylenecyclohexane and 5-methylene-1,3-dioxane systems suggest that two electronic factors contribute to the stereoselectivity of epoxidation and diimide reduction. These are respectively the spatial anisotropy of the HOMO with respect to the two faces of the double bond, common to both molecules, which is likely to be responsible for the overall axial stereofacial selectivity exhibited, and a similar anisotropy in the electrostatic potential field of the methylenedioxane caused by the oxygens; which also favours attack from an axial direction by polarisable electrophilic species. The anisotropy of the HOMO arises from the important topological difference between the contributions made to the HOMO by the periplanar β C–H σ bonds and opposing β C–O or C–C σ bonds. Catalytic reduction proceeds with equatorial face selectivity for both the cyclohexane and the dioxane systems and appears to be governed largely by steric effects.

  对亚甲基环己烷和 5-亚甲基-1,3-二氧六环体系进行的加成反应研究和 ab initio 计算表明，两个电子因素有助于环氧化和二亚胺还原的立体选择性。这两个因素分别是：HOMO 相对于双键两个面的空间各向异性（这是两个分子共有的），这可能是表现出的整体轴向立体选择性的原因；由氧原子引起的亚甲基二氧杂环己烷静电势场的类似各向异性；这也有利于可极化亲电物种从轴向进行攻击。HOMO 的各向异性源于周面 β C-H σ 键和对立的 β C-O 或 C-C σ 键对 HOMO 的贡献存在重要的拓扑差异。环己烷和二氧杂环烷体系的催化还原过程具有赤道面选择性，似乎主要受立体效应的影响。
• Efficient synthesis of various acycloalkenyl derivatives of pyrimidine using cross-metathesis and Pd(0) methodologies
  作者：Franck Amblard、Steven P. Nolan、Raymond F. Schinazi、Luigi A. Agrofoglio

  DOI：10.1016/j.tet.2004.11.019

  日期：2005.1

  Novel acyclonucleosides (9a-d, 10a-d, 18a,b and 19a,b) have been prepared using Pd(0) and cross-metathesis methodologies. The allylic N-alkylation under Tsuji-Trost conditions was used to introduce the nucleobase, while the Suzuki-Miyaura reaction afforded C-5 substituted uracil analogues. The cross-metathesis performed with a ruthenium catalyst was used to provide new acycloalkenyl nucleosides. The antiviral activities of all final compounds have been evaluated. (C) 2004 Elsevier Ltd. All rights reserved.
• Weiss,F. et al., Bulletin de la Societe Chimique de France, 1965, p. 1358 - 1364
  作者：Weiss,F. et al.

  DOI：——

  日期：——