2,2-dimethyltridec-4-yn-3-one | 139313-50-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-dimethyltridec-4-yn-3-one
• CAS: 139313-50-1
• 化学式: C₁₅H₂₆O
• 分子量: 222.371
• InChiKey: XVKCCRCIQKVMPK-UHFFFAOYSA-N

物化性质

• 沸点：
  301.5±25.0 °C(Predicted)
• 密度：
  0.866±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,2-dimethyltridec-4-yn-3-one 在 (-)-diisopinocamphenylborane chloride 作用下， 以 neat (no solvent) 为溶剂， 反应 20.0h， 以77%的产率得到4-十三碳炔-3-醇,2,2-二甲基-,(R)-
  参考文献：
  名称：

  Chiral synthesis via organoboranes. 34. Selective reductions. 47. Asymmetric reduction of hindered .alpha.,.beta.-acetylenic ketones with B-chlorodiisopinocampheylborane to propargylic alcohols of very high enantiomeric excess. Improved workup procedure for the isolation of product alcohols

  摘要：

  The Midland reagent, Alpine-Borane (2a), is excellent for the asymmetric reduction of many acetylenic ketones, but it fails with hindered derivatives. On the other hand, B-chlorodiisopinocampheylborane (DIP-Chloride, 4) reacts with hindered alpha,beta-acetylenic ketones to provide the corresponding propargylic alcohols in 96 to greater-than-or-equal-to 99% ee. The reaction is in accordance with the tentative mechanism proposed earlier. While 4-phenyl-3-butyn-2-one is reduced in only 21% ee, 4 reduces 4-methyl-1-phenyl-1-pentyn-3-one in 53% ee and 4,4-dimethyl-1-phenyl-1-pentyn-3-one in greater-than-or-equal-to 99% ee. The generality of this observation is demonstrated by reducing a series of hindered acetylenic ketones with increasing steric requirements and differing electronic environments. Thus, 2,2-dimethyl-4-tridecyn-3-one, 1-cyclopentyl-4,4-dimethyl-1-pentyn-3-one, and 3,3-dimethyl-5-tetradecyn-4-one are all reduced to the corresponding alcohols in greater-than-or-equal-to 99% ee and 97% ee, respectively. A modified and operationally simpler workup procedure for obtaining the alcohols in high isolated yields is described. Comparison of reagent 4 with 2a is also made, making clear the range of applicability of each reagent. This development makes it possible to reduce asymmetrically any acetylenic ketone by a judicious choice of either 2a or 4.

  DOI：

  10.1021/jo00034a034
• 作为产物：
  描述：

  C₁₅H₂₈O 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 以1.98 g的产率得到2,2-dimethyltridec-4-yn-3-one
  参考文献：
  名称：

  钌催化的 Ynones 硼氢化导致非传统的反应模式

  摘要：

  尽管简单的酮和炔烃的硼氢化作用已经得到很好的证实，但对于重要组成部分 ynones 的独特硼氢化反应活性知之甚少。在这里，我们报告了一种新的 ynone 反应模式，在温和的钌催化硼氢化条件下，产生了结构新颖且合成有用但以前无法获得的产品，即 α-羟基硼酸乙烯酯。尽管存在许多可能的竞争途径，但该反应具有高效、范围广和完全的化学选择性、区域选择性和立体选择性。对照实验和详细的 DFT 研究都提出了一个两步机制，包括初始速率决定共轭添加氢硼烷以形成关键的硼基丙二烯酸中间体，然后对丙二烯酸的烯醇基序进行快速的第二次硼氢化。尤其，氢硼烷与羰基共轭炔烃的直接 1,4-加成反应也代表了一种新的反应模式。尽管这个过程极其复杂，几乎每一步都涉及选择性控制，但对大量可能的过渡态的彻底而详细的计算解释了不寻常的反应性和选择性的内在起源。

  DOI：

  10.1021/jacs.2c06024

文献信息

• 烯基取代-α-羟基硼酸酯化合物的制备方法
  申请人：香港科技大学深圳研究院

  公开号：CN115322211A

  公开（公告）日：2022-11-11

  本申请涉及合成化学技术领域，尤其涉及一种烯基取代‑α‑羟基硼酸酯化合物的制备方法，包括以下步骤：将式I所示的α,β‑不饱和炔酮化合物和式II所示的频哪醇硼烷在催化剂条件下进行硼氢化反应，得到式III所示的烯基取代‑α‑羟基硼酸酯化合物；该制备方法具有反应选择性专一、副反应少、效率高的特点，在合成化学领域具有很高的应用价值。
• Chiral synthesis via organoboranes. 34. Selective reductions. 47. Asymmetric reduction of hindered .alpha.,.beta.-acetylenic ketones with B-chlorodiisopinocampheylborane to propargylic alcohols of very high enantiomeric excess. Improved workup procedure for the isolation of product alcohols
  作者：P. Veeraraghavan Ramachandran、Aleksandar V. Teodorovic、Milind V. Rangaishenvi、Herbert C. Brown

  DOI：10.1021/jo00034a034

  日期：1992.4

  The Midland reagent, Alpine-Borane (2a), is excellent for the asymmetric reduction of many acetylenic ketones, but it fails with hindered derivatives. On the other hand, B-chlorodiisopinocampheylborane (DIP-Chloride, 4) reacts with hindered alpha,beta-acetylenic ketones to provide the corresponding propargylic alcohols in 96 to greater-than-or-equal-to 99% ee. The reaction is in accordance with the tentative mechanism proposed earlier. While 4-phenyl-3-butyn-2-one is reduced in only 21% ee, 4 reduces 4-methyl-1-phenyl-1-pentyn-3-one in 53% ee and 4,4-dimethyl-1-phenyl-1-pentyn-3-one in greater-than-or-equal-to 99% ee. The generality of this observation is demonstrated by reducing a series of hindered acetylenic ketones with increasing steric requirements and differing electronic environments. Thus, 2,2-dimethyl-4-tridecyn-3-one, 1-cyclopentyl-4,4-dimethyl-1-pentyn-3-one, and 3,3-dimethyl-5-tetradecyn-4-one are all reduced to the corresponding alcohols in greater-than-or-equal-to 99% ee and 97% ee, respectively. A modified and operationally simpler workup procedure for obtaining the alcohols in high isolated yields is described. Comparison of reagent 4 with 2a is also made, making clear the range of applicability of each reagent. This development makes it possible to reduce asymmetrically any acetylenic ketone by a judicious choice of either 2a or 4.
• Ru-Catalyzed Hydroboration of Ynones Leads to a Nontraditional Mode of Reactivity
  作者：Qiang Feng、Shijia Li、Zhiyang Li、Qiaolin Yan、Xiangfeng Lin、Lijuan Song、Xinhao Zhang、Yun-Dong Wu、Jianwei Sun

  DOI：10.1021/jacs.2c06024

  日期：2022.8.17

  initial rate-determining conjugate addition of hydroborane to form the key boryl allenolate intermediate followed by a fast second hydroboration of the enolate motif of the allenolate. Notably, direct 1,4-addition of hydroborane to carbonyl-conjugated alkynes also represents a new mode of reactivity. Despite the overwhelming complexity of this process, which involves selectivity control in almost every step

  尽管简单的酮和炔烃的硼氢化作用已经得到很好的证实，但对于重要组成部分 ynones 的独特硼氢化反应活性知之甚少。在这里，我们报告了一种新的 ynone 反应模式，在温和的钌催化硼氢化条件下，产生了结构新颖且合成有用但以前无法获得的产品，即 α-羟基硼酸乙烯酯。尽管存在许多可能的竞争途径，但该反应具有高效、范围广和完全的化学选择性、区域选择性和立体选择性。对照实验和详细的 DFT 研究都提出了一个两步机制，包括初始速率决定共轭添加氢硼烷以形成关键的硼基丙二烯酸中间体，然后对丙二烯酸的烯醇基序进行快速的第二次硼氢化。尤其，氢硼烷与羰基共轭炔烃的直接 1,4-加成反应也代表了一种新的反应模式。尽管这个过程极其复杂，几乎每一步都涉及选择性控制，但对大量可能的过渡态的彻底而详细的计算解释了不寻常的反应性和选择性的内在起源。