(R)-4-ethynyl-2,2-dimethyl-1,3-dioxane | 1023661-09-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-4-ethynyl-2,2-dimethyl-1,3-dioxane
• 英文别名: (4R)-4-ethynyl-2,2-dimethyl-1,3-dioxane
• CAS: 1023661-09-7
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: XFBGMPJITOZKRD-ZETCQYMHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  (R)-4-ethynyl-2,2-dimethyl-1,3-dioxane 、 (4S)-4-tert-butoxy-3,4-dihydro-2H-pyrrole 1-oxide 在 copper(l) iodide 、 三乙胺 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以55%的产率得到(4S,5R,6S)-6-[(4R)-2,2-dimethyl-1,3-dioxan-4-yl]-4-[(2-methylpropan-2-yl)oxy]-1-azabicyclo[3.2.0]heptan-7-one
  参考文献：
  名称：

  通过环加成/重排级联反应直接催化合成碳青霉烯：意外的乙炔结构效应

  摘要：

  衍生自甘油醛和炔丙基醛的乙炔的反应在Cu（I）离子催化的Kinugasa环加成/重排级联过程中显示出显着的反应性。反应通过形成刚性双核铜（I）配合物而进行，其中每个铜离子与乙炔分子中的一个或两个氧原子以及两个三键配位。已经证明，一个氧原子可以被苯环取代，该苯环能够通过芳族六聚体配位铜离子。还可以在催化量的铜盐存在下进行高产率的Kinugasa反应，以提供可接受的产率而不降低非对映选择性的产物。

  DOI：

  10.1021/jo101355h
• 作为产物：
  描述：

  methyl (4R)-2,2-dimethyl-1,3-dioxane-4-carboxylate 在 二异丁基氢化铝 作用下， 生成 (R)-4-ethynyl-2,2-dimethyl-1,3-dioxane
  参考文献：
  名称：

  Diastereoselective synthesis of β-lactams via Kinugasa reaction of acyclic chiral nitrones

  摘要：

  An approach to beta-lactams via a Kinugasa reaction between chiral copper acetylides and chiral acyclic nitrones bearing either 1,3-dioxane or 1,3-dioxolane moieties is reported. The stereochemical preferences observed in these reactions are discussed. The reaction provides access to a variety of interesting beta-lactam structures. Electronic circular dichroism in combination with NMR spectroscopy was shown to be a useful and effective method for the reliable determination of the absolute configuration of all components of a complex mixtures of azetidinones. The effectiveness of the chiral analysis of complex mixtures was demonstrated for HPLC coupled on-line with electronic circular dichroism detection as well. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2015.11.006

文献信息

• Modular Synthesis of the C9−C27 Degradation Product of Aflastatin A via Alkyne−Epoxide Cross-Couplings
  作者：Omar Robles、Frank E. McDonald

  DOI：10.1021/ol800659z

  日期：2008.5.1

  A modular approach to the synthesis of complex polyketide natural products is demonstrated for the synthesis of the C9-C27 degradation product from aflastatin A. The product of the cross-coupling of C23-C27 terminal alkyne with C17-C22 epoxide underwent functionalization of the resulting internal alkyne, which was then coupled similarly with C9-C16 epoxide. This synthesis concluded with regio- and

  证明了从复杂的聚酮化合物天然产物合成的模块化方法，用于从黄素抑素A合成C9-C27降解产物。C23-C27末端炔烃与C17-C22环氧化合物的交叉偶联产物经过官能化处理内部炔烃，然后将其与C9-C16环氧类似地偶联。该合成结束于将甲基区域内和立体选择性加成到内部炔烃上，然后进行立体选择性加氢硼化-氧化。
• [EN] METHOD FOR PREPARING INGENOL-3-HEXANOATE, METHOD FOR PREPARING 3-ETHYNYL-3-HYDROXY-4,7,7-TRIMETHYLBICYCLO[4.1.0]HEPTANE-2-CARBALDEHYDE, AND METHOD FOR PREPARING THE COMPOUND 2,2-DIMETHYL-4-ETHYNYL-5-TRIPHENYLPHOSPHORUS ANYLIDENE-1,3-DIOXANE<br/>[FR] PROCÉDÉ DE PRÉPARATION D'INGÉNOL-3-HEXANOATE, PROCÉDÉ DE PRÉPARATION DE 3-ÉTHYNYL-3-HYDROXY-4.7.7-TRIMÉTHYLBICYCLO[4.1.0]HEPTANE-2-CARBALDÉHYDE ET PROCÉDÉ DE PRÉPARATION DU COMPOSÉ 2,2-DIMÉTHYL-4-ÉTHYNYL-5-TRIPHÉNYLPHOSPHORANYLIDÈNE-1,3-DIOXANE<br/>[PT] MÉTODO DE PREPARAÇÃO DE INGENOL-3-HEXANOATO, MÉTODO DE PREPARAÇÃO DE 3-ETINIL-3-HIDROXI-4.7.7-TRIMETILBICICLO[4.1.0]HEPTANO-2-CARBALDEÍDO E MÉTODO DE PREPARAÇÃO DO COMPOSTO 2,2-DIMETIL-4-ETINIL-5-TRIFENILFOSFORANILIDENO-1,3-DIOXANO
  申请人：AMAZÔNIA FITOMEDICAMENTOS LTDA

  公开号：WO2016191837A1

  公开（公告）日：2016-12-08

  A presente invenção refere-se a método de preparação de ingenol-3-hexanoato assim como ingenol-3-hexanoato obtido por tal processo.

  这个发明涉及一种制备3-己酸基-英吉利醇的方法，以及通过该方法获得的3-己酸基-英吉利醇。
• Direct, Catalytic Synthesis of Carbapenams via Cycloaddition/Rearrangement Cascade Reaction: Unexpected Acetylenes’ Structure Effect
  作者：Adam Mames、Sebastian Stecko、Paulina Mikołajczyk、Magdalena Soluch、Bartłomiej Furman、Marek Chmielewski

  DOI：10.1021/jo101355h

  日期：2010.11.19

  Reactions of acetylenes derived from glyceraldehyde and propargyl aldehyde show remarkable reactivity in Kinugasa cycloaddition/rearrangement cascade process catalyzed by Cu(I) ion. Reactions proceed by formation of a rigid dinuclear copper(I) complex in which each copper ion is coordinated to one or both oxygen atoms in the acetylene molecule and to both triple bonds. It has been demonstrated that

  衍生自甘油醛和炔丙基醛的乙炔的反应在Cu（I）离子催化的Kinugasa环加成/重排级联过程中显示出显着的反应性。反应通过形成刚性双核铜（I）配合物而进行，其中每个铜离子与乙炔分子中的一个或两个氧原子以及两个三键配位。已经证明，一个氧原子可以被苯环取代，该苯环能够通过芳族六聚体配位铜离子。还可以在催化量的铜盐存在下进行高产率的Kinugasa反应，以提供可接受的产率而不降低非对映选择性的产物。
• Diastereoselective synthesis of β-lactams via Kinugasa reaction of acyclic chiral nitrones
  作者：Łukasz Mucha、Kamil Parda、Olga Staszewska-Krajewska、Sebastian Stecko、Artur Ulikowski、Jadwiga Frelek、Agata Suszczyńska、Marek Chmielewski、Bartłomiej Furman

  DOI：10.1016/j.tetasy.2015.11.006

  日期：2016.1

  An approach to beta-lactams via a Kinugasa reaction between chiral copper acetylides and chiral acyclic nitrones bearing either 1,3-dioxane or 1,3-dioxolane moieties is reported. The stereochemical preferences observed in these reactions are discussed. The reaction provides access to a variety of interesting beta-lactam structures. Electronic circular dichroism in combination with NMR spectroscopy was shown to be a useful and effective method for the reliable determination of the absolute configuration of all components of a complex mixtures of azetidinones. The effectiveness of the chiral analysis of complex mixtures was demonstrated for HPLC coupled on-line with electronic circular dichroism detection as well. (C) 2015 Elsevier Ltd. All rights reserved.