(R)-3,4-O-isopropylidene-3,4-dihydroxybutyne | 186521-82-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-3,4-O-isopropylidene-3,4-dihydroxybutyne
• 英文别名: (R)-3,4-Dihydroxybutyne acetonide；(R)-(-)-4-Ethynyl-2,2-dimethyl-1,3-dioxolane；(R)-(2,2-dimethyl-1,3-dioxolan-4-yl)acetylene；(4R)-4-ethynyl-2,2-dimethyl-1,3-dioxolane；2,2-dimethyl-4(R)-ethynyl-1,3-dioxolane
• CAS: 186521-82-4
• 化学式: C₇H₁₀O₂
• 分子量: 126.155
• InChiKey: GPNBPQQQZHDRMZ-ZCFIWIBFSA-N

物化性质

• 沸点：
  129.6±35.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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)-3,4-O-isopropylidene-3,4-dihydroxybutyne 在 正丁基锂 、 水 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  [EN] MULTICYCLIC COMPOUNDS
  [FR] COMPOSÉS MULTICYCLIQUES

  摘要：

  Compounds of Formulae (I), (II) and (III), including pharmaceutically acceptable salts are described herein. Such compounds, as well as pharmaceutically acceptable salts and compositions thereof, are useful for treating diseases or conditions a disease or disorder that can be treated with a KOR agonist and/or MOR agonist. Compounds described herein, along with pharmaceutically acceptable salts and compositions thereof, can be used to alleviate at least one symptom of the disease or disorder described herein.

  公开号：

  WO2023086580A2
• 作为产物：
  描述：

  (S)-(-)-2,2-二甲基-1,3-二氧戊环-4-羧酸甲酯 在 二异丁基氢化铝 作用下， 生成 (R)-3,4-O-isopropylidene-3,4-dihydroxybutyne
  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

• [EN] A PROCESS FOR THE PREPARATION OF AN ALDEHYDE BETA-LACTAM COMPOUND<br/>[FR] PROCÉDÉ DE PRÉPARATION D'UN COMPOSÉ BÊTA-LACTAME D'ALDÉHYDE
  申请人：ADAMED SP ZOO

  公开号：WO2010097350A1

  公开（公告）日：2010-09-02

  The invention relates to a process for the preparation of an aldehyde beta-lactam compound of formula (I), wherein P1 is H or a protecting group, useful in the preparation of ezetimibe, from a nitrone compound of formula (II). The nitrone compound Il is prepared by reacting 4-fluorophenylhydroxyloamine with OH- protected 4-hydroxybenzaldehyde. The nitrone compound of formula (II) is reacted with an acetylene compound of formula (III) to form a compound of formula (IV), and the compound of formula (IV), after optional deprotection, is oxidized to obtain an aldehyde of formula (V), which undergoes isomerisation to the compound of formula (I). The subject of the invention are also novel compounds of formulas (II) and (IV).

  本发明涉及一种用于制备公式（I）所示的醛基β-内酰胺化合物的方法，其中P1是H或一个保护基团，该方法可用于依泽替米滨的制备，从公式（II）所示的硝酮化合物出发。硝酮化合物II是通过4-氟苯基羟基胺与OH-保护的4-羟基苯甲醛反应制备的。公式（II）所示的硝酮化合物与公式（III）所示的炔烃化合物反应，形成公式（IV）的化合物，公式（IV）的化合物在可选去保护后，被氧化以获得公式（V）的醛，该醛经过异构化转变为公式（I）的化合物。本发明的主题还包括新颖的公式（II）和（IV）的化合物。
• An Entry to the Carbapenem Antibiotic Scaffold via the Asymmetric Kinugasa Reaction
  作者：Marek Chmielewski、Magdalena Maciejko、Sebastian Stecko、Olga Staszewska-Krajewska、Margarita Jurczak、Bartłomiej Furman

  DOI：10.1055/s-0032-1316732

  日期：——

  entry toward thienamycin and related compounds. The copper(I)-mediated reaction between five-membered cyclic nitrones and terminal acetylenes, leading to the assembly of the basic skeleton of carbapenem antibiotics is described. The diastereoselectivity of this cycloaddition–rearrangement cascade, a process known as the Kinugasa reaction, with respect to the structure and configuration of both substrates

  摘要 描述了五元环硝酮与末端乙炔之间的铜（I）介导的反应，导致碳青霉烯抗生素基本骨架的组装。讨论了这种环加成-重排级联的非对映选择性，该过程称为Kinugasa反应，涉及两种底物的结构和构型以及反应条件。所描述的方法在糖衍生的硝酮上的应用为硫霉素和相关化合物提供了有吸引力的入口。 描述了五元环硝酮与末端乙炔之间的铜（I）介导的反应，导致碳青霉烯抗生素基本骨架的组装。讨论了这种环加成-重排级联的非对映选择性，该过程称为Kinugasa反应，涉及两种底物的结构和构型以及反应条件。所描述的方法在糖衍生的硝酮上的应用为硫霉素和相关化合物提供了有吸引力的入口。
• Total synthesis of both enantiomers of melodorinol. Redetermination of their absolute configurations
  作者：Xiyan Lu、Guoying Chen、Lijun Xia、Guangzhong Guo

  DOI：10.1016/s0957-4166(97)00373-x

  日期：1997.9

  Both enantiomers of the natural products, melodorinol and acetylmelodorinol, have been synthesized by a palladium catalyzed enyne coupling methodology. Their absolute configuration aare redetermined.

  通过钯催化的烯炔偶联方法合成了天然产物美德诺醇和乙酰基美德诺醇的两种对映异构体。重新确定了它们的绝对配置。
• The use of carbonyl group anisotropy effect in determination of the relative configuration of carbapenams
  作者：Olga Staszewska-Krajewska、Wojciech Bocian、Magdalena Maciejko、Piotr Szcześniak、Krzysztof Szymczak、Marek Chmielewski、Bartłomiej Furman

  DOI：10.3998/ark.5550190.p008.450

  日期：——

  shifts of the H-2 proton and geminal protons of the protected alkoxymethyl group at the C-2 carbon atom. The differences of 1 H NMR chemical shifts of these protons fall in two ranges of about 3.3-3.7 ppm, and 4.0-4.4 ppm. This observation can be attributed to the influence of the anisotropy of the neighboring carbonyl group and can be easily correlated with configuration at the bridgehead carbon atom

  通过分析 C-2 碳上受保护的烷氧基甲基的 H-2 质子和孪生质子的化学位移，可以很容易地确定在 Kinugasa 反应中获得的双环碳青霉烯的桥头碳原子处新形成的立体中心的相对构型原子。这些质子的 1 H NMR 化学位移的差异落在约 3.3-3.7 ppm 和 4.0-4.4 ppm 的两个范围内。这种观察可以归因于相邻羰基各向异性的影响，并且可以很容易地与桥头碳原子的构型相关联。
• First application of fluorinated nitrones for the synthesis of fluoroalkylated β-lactams via the Kinugasa reaction
  作者：Marcin K. Kowalski、Grzegorz Mlostoń、Emilia Obijalska、Anthony Linden、Heinz Heimgartner

  DOI：10.1016/j.tet.2016.06.073

  日期：2016.9

  The regioselective reactions of fluorinated nitrones with selected terminal alkynes (Kinugasa reaction) was studied in the presence of Cu(I) iodide and TEA as a base. After chromatographic purification the desired β-lactams were obtained in high yields (up to 93%) and high diastereoselectivities (up to 9:1). The reactions performed in the presence of chiral, enantiomerically pure ligands led to enantiomerically

  在碘化铜（I）和TEA为碱的情况下，研究了氟化硝酮与选定的末端炔烃的区域选择性反应（Kinugasa反应）。色谱纯化后，以高收率（最高93％）和高非对映选择性（最高9：1）获得所需的β-内酰胺。在手性，对映体纯配体的存在下进行的反应导致获得对映体富集的产物（ee值高达26％），这可能是非对映异构体之一，具体取决于所使用的手性配体的类型。