2-tert-butyl-5-methylene-1,3-dioxane | 26170-12-7

• 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: 2-tert-butyl-5-methylene-1,3-dioxane
• 英文别名: 2-Tert-butyl-5-methylidene-1,3-dioxane
• CAS: 26170-12-7
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: QNFQQXKVWXCEIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-tert-butyl-5-methylene-1,3-dioxane 以90%的产率得到
  参考文献：
  名称：

  Vadecard Jerome, Plaquevent Jean-Christophe, Duhamel Lucette, Duhamel Pie+, J. Org. Chem, 59 (1994) N 9, S 2285-2286

  摘要：

  DOI：

文献信息

• 5-Methyl-4H-1,3-dioxins, new chiral building blocks: transformation into (R)- and (S)-4-hydroxymethyl-4-methyl-1,3-dioxolanes via oxidation and rearrangement and determination of the absolute configuration
  作者：Susanne Flock、Herbert Frauenrath、Carsten Wattenbach

  DOI：10.1016/j.tetasy.2005.08.046

  日期：2005.10

  stereochemical course of this transformation has been studied, while the relative configuration of the intermediate oxidation product and the absolute configuration of the resulting camphanyl ester of 2-tert-butyl-4-hydroxymethyl-4-methyl-1,3-dioxolane was established by X-ray crystallography. From these results, the absolute configuration of the dioxins has been deduced.

  5-甲基-4- ħ -1,3-二恶英通过不对称双键异构化获得的已经转变为4-羟甲基-4-甲基-1,3-二氧戊环由米氯过苯甲酸氧化，环收缩和减少。研究了这种转变的立体化学过程，同时确定了中间氧化产物的相对构型和所得的2-叔丁基-4-羟甲基-4-甲基-1,3-二氧戊环樟脑酯的绝对构型通过X射线晶体学。从这些结果，已经推断出二恶英的绝对构型。
• 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。
• Scissions sigmatropiques d'acétals non saturés
  作者：F. Mutterer、J.M. Morgen、J.M. Biedermann、J.P. Fleury、F. Weiss

  DOI：10.1016/s0040-4020(01)97844-5

  日期：1970.1
• Ishiyama, Jun-ichi; Senda, Yasuhisa; Imaizumi, Shin, Journal of the Chemical Society. Perkin transactions II, 1982, p. 71 - 76
  作者：Ishiyama, Jun-ichi、Senda, Yasuhisa、Imaizumi, Shin

  DOI：——

  日期：——
• Asymmetric double-bond isomerization of cyclic allyl acetals by using diop and chiraphos modified nickel complexes
  作者：Herbert Frauenrath、Stefan Reim、Astrid Wiesner

  DOI：10.1016/s0957-4166(98)00101-3

  日期：1998.4

  Diop or chiraphos modified dibromo- and dichloronickel complexes proved to be readily available catalyst precursors, which upon activation with lithium triethylborohydride (Super-Hydride(R)) gave enantioselectivities up to 92% ee for the asymmetric isomerization of 5-methylene-1,3-dioxanes 3 and up to 67% ee for the asymmetric isomerization of 4,7-dihydro-1,3-dioxepins 1. (C) 1998 Elsevier Science Ltd. All rights reserved.