4,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2-one | 1175712-38-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: 4,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2-one
• 英文别名: 4,4-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2-one
• CAS: 1175712-38-5
• 化学式: C₁₆H₃₀B₂O₅
• 分子量: 324.033
• InChiKey: UQVLQUWSAZLMIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.06
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  4,8-dimethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,6,2-dioxazaborocane 、 3-丁炔-2-酮 在 copper(l) chloride 、 2,2,2-三氟乙醇 作用下， 以 二氯甲烷 为溶剂， 反应 3.08h， 以79%的产率得到4,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2-one
  参考文献：
  名称：

  Structure and Reactivity of a Preactivated sp²–sp³ Diboron Reagent: Catalytic Regioselective Boration of α,β-Unsaturated Conjugated Compounds

  摘要：

  A novel sp(2)-sp(3) diboron reagent has been developed for the copper-catalyzed beta-boration of alpha,beta-unsaturated conjugated compounds. The reaction proceeds under mild conditions with various substrates, i.e., alpha,beta-unsaturated esters, ketones, nitriles, ynones, amides, and aldehydes, in the absence of additives such as phosphine and sodium tert-butoxide to provide beta-borylhomoenolates in good to excellent yields. The presence of an sp(3)-hybridized boron center, un-ambigously confirmed by X-ray crystallography, sufficiently activates the unsymmetrical pinacolato diisopropanolaminato diboron (PDIPA diboron, 2) to transfer the sp(2)-hybridized boron moiety chemoselectively. These observations suggest that the activation of one of the boron atoms is an essential step in the Cu-catalyzed beta-boration catalytic cycle.

  DOI：

  10.1021/jo2003488

文献信息

• sp²−sp³ Hybridized Mixed Diboron: Synthesis, Characterization, and Copper-Catalyzed β-Boration of α,β-Unsaturated Conjugated Compounds
  作者：Ming Gao、Steven B. Thorpe、Webster L. Santos

  DOI：10.1021/ol901359n

  日期：2009.8.6

  A novel sp2−sp3 hybridized mixed diboron and its reactivity on the copper-catalyzed β-boration of α,β-unsaturated conjugated compounds to afford the corresponding β-borated compounds is reported. The presence of sp3-hybridized boron provides a mild β-boration condition in the absence of phosphine and base additives. Finally, our investigations demonstrate that the sp2-hybridized boron of the mixed

  报道了一种新颖的sp 2 -sp 3杂交的混合二硼及其在α，β-不饱和共轭化合物的铜催化的β-硼酸酯上的反应性，从而提供了相应的β-硼酸酯化的化合物。sp 3-杂化硼的存在在没有膦和碱添加剂的情况下提供了温和的β-硼化条件。最后，我们的研究表明混合二硼的sp 2-杂化硼被选择性转移到共轭底物的β-碳上。
• A copper nitride nanocube catalyst for highly efficient hydroboration of alkynes
  作者：Hang Xu、Sho Yamaguchi、Takato Mitsudome、Tomoo Mizugaki

  DOI：10.1039/d2ob02130g

  日期：——

  is a useful method for the synthesis of vinyl boronate esters, which are essential intermediates in organic syntheses. Copper catalysts have been used extensively in these reactions. However, previously reported Cu-catalyst systems inevitably require additives and elevated temperatures. Herein, we report, for the first time, a simple and efficient hydroboration of alkynes under additive-free and mild

  炔烃与双（频哪醇）二硼的硼氢化反应是合成乙烯基硼酸酯的有用方法，乙烯基硼酸酯是有机合成中必不可少的中间体。铜催化剂已广泛用于这些反应。然而，先前报道的铜催化剂系统不可避免地需要添加剂和高温。在此，我们首次报道了使用氮化铜纳米立方体 (Cu 3 N NC) 催化剂在无添加剂和温和反应条件下（即在 30 °C 的温度下）简单有效的炔烃硼氢化反应。多种炔烃可以转化为相应的硼酸酯。铜3N NCs也适用于炔烃与四羟基二硼的硼氢化反应合成乙烯基硼酸。此外，Cu 3 N NCs 很容易通过简单的过滤分离，并且可以重复使用多次而不会损失其原有的活性。因此，这些高活性和可重复使用的 Cu 3 N NC 催化剂为高效生产硼酸乙烯酯提供了一条环保途径。
• Structure and Reactivity of a Preactivated sp²–sp³ Diboron Reagent: Catalytic Regioselective Boration of α,β-Unsaturated Conjugated Compounds
  作者：Ming Gao、Steven B. Thorpe、Christian Kleeberg、Carla Slebodnick、Todd B. Marder、Webster L. Santos

  DOI：10.1021/jo2003488

  日期：2011.5.20

  A novel sp(2)-sp(3) diboron reagent has been developed for the copper-catalyzed beta-boration of alpha,beta-unsaturated conjugated compounds. The reaction proceeds under mild conditions with various substrates, i.e., alpha,beta-unsaturated esters, ketones, nitriles, ynones, amides, and aldehydes, in the absence of additives such as phosphine and sodium tert-butoxide to provide beta-borylhomoenolates in good to excellent yields. The presence of an sp(3)-hybridized boron center, un-ambigously confirmed by X-ray crystallography, sufficiently activates the unsymmetrical pinacolato diisopropanolaminato diboron (PDIPA diboron, 2) to transfer the sp(2)-hybridized boron moiety chemoselectively. These observations suggest that the activation of one of the boron atoms is an essential step in the Cu-catalyzed beta-boration catalytic cycle.