borane-D3-THF complex

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: borane-D3-THF complex
• 英文别名: [(2)H]borane - tetrahydrofuran (1/1)；Borane-D3 (D, 98%) (1 M in THF) (+0.005M NaBD4)；oxolane;trideuterioborane
• 化学式: BH₃*C₄H₈O
• 分子量: 88.9179
• InChiKey: RMCYTHFAWCWRFA-SVLQTQOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.39
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  borane-D3-THF complex 、 氨 以 tetrahydrofuran 为溶剂， 生成 borane-ammonia-d3
  参考文献：
  名称：

  氨硼烷及其氘代化合物中的四方相到正​​交相变

  摘要：

  摘要 利用非弹性光谱和差示扫描量热法表征了氨硼烷中发生的四方相到正​​交相变。转变是一阶的，因为在相转变过程中产生了可观的潜热；然而，转变也具有二级特征，正如在转变温度以上开始显着的模量软化所证明的那样；提出了一种解释这种转变的物理机制。动态杨氏模量的直接逐步监测使我们能够观察到冷却和加热之间的实际温度滞后相当小（~0.4 K），并且完全转变以开尔文的一小部分演变，并且存在等离子。相位波动。

  DOI：

  10.1016/j.jallcom.2010.10.217
• 作为产物：
  描述：

  四氢呋喃 在 diborane-d6 作用下， 生成 borane-D3-THF complex
  参考文献：
  名称：

  新型胺稳定的氘代硼烷-四氢呋喃配合物（BD 3 -THF）：掺入氘的便捷试剂

  摘要：

  开发了方便的BD 3 -THF配合物的制备方法。某些胺可稳定BD 3 -THF以长期保存。使用具有代表性烯烃的新型胺稳定BD 3 -THF进行了区域选择性研究。烯烃的氢硼化为氧化后制备相应的氘代醇提供了方便的工具。

  DOI：

  10.1016/j.tetlet.2007.01.134
• 作为试剂：
  描述：

  1,3-双(2,6-二异丙基苯基)氯化咪唑鎓 在 potassium tert-butylate 、 borane-D3-THF complex 作用下， 以 四氢呋喃 为溶剂， 反应 16.17h， 以60%的产率得到(1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-3-ium-2-yl)borate-d3
  参考文献：
  名称：

  Complexes of Borane and N-Heterocyclic Carbenes: A New Class of Radical Hydrogen Atom Donor

  摘要：

  Calculations suggest that complexes of borane with N-heterocyclic carbenes (NHC) have B-H bond dissocation energies more then 20 Kcal/mol less than free borane, diborane, borane-THF, and related complexes. Values are in the range of popular radical hydrogen atom donors like tin hydrides (70-80 Kcal/mol). The resulting prediction that NHC borane complexes could be used as radical hydrogen atom donors was verified by radical deoxygenations of xanthates by using either AIBN or triethylborane as initiator.

  DOI：

  10.1021/ja804150k

文献信息

• Transition Metal-Free <i>Trans</i> Hydroboration of Alkynoic Acid Derivatives: Experimental and Theoretical Studies
  作者：Russell Fritzemeier、Ashley Gates、Xueying Guo、Zhenyang Lin、Webster L. Santos

  DOI：10.1021/acs.joc.8b01493

  日期：2018.9.7

  (E)-β-boryl acrylamides in good to excellent yields. The reaction is tolerant of a variety of functional groups and allows efficient access to novel oxaboroles as well as a pargyline derivative (MAO inhibitor). Theoretical calculations suggest an internal hydride generates a phosphonium allenoxyborane followed by the formation of a key phosphonocyclobutene intermediate that collapses in a stereoselective

  我们报告了膦酸酯催化的炔烃酯和酰胺的反式氢硼化。该反应在温和的条件下以排他的（E）选择性进行，以良好至极好的收率得到（E）-β-硼基丙烯酸酯和（E）-β-硼基丙烯酰胺。该反应可耐受多种官能团，并可以有效地获得新的草并五氢硼烷以及一种精氨酸衍生物（MAO抑制剂）。理论计算表明，内部氢化物会生成all烯丙氧基硼烷，然后形成关键的膦酰基环丁烯中间体，该中间体在立体选择性的限速步骤中会崩溃。
• Vinylborane Formation in Rhodium-Catalyzed Hydroboration of Vinylarenes. Mechanism versus Borane Structure and Relationship to Silation
  作者：John M. Brown、Guy C. Lloyd-Jones

  DOI：10.1021/ja00082a006

  日期：1994.2

  Attempted catalytic hydroboration of (4-methoxyphenyl)ethene 1 with R,R-3-isopropyl-4-methyl-5-phenyl-1,3,2-oxazaborolidine 6 proceeded extremely slowly relative to the 3-methyl analog 2 derived from φ-ephedrine when diphosphinerhodium complexes were employed. With phosphine-free rhodium catalysts, especially the 4-methoxyphenylethene complex 7, the reaction proceeded rapidly and quantitatively to

  (4-甲氧基苯基)乙烯 1 与 R,R-3-isopropyl-4-methyl-5-phenyl-1,3,2-oxazaborolidine 6 的催化硼氢化反应相对于衍生自 φ 的 3-甲基类似物 2 进行得非常缓慢- 麻黄碱，当使用二膦铑配合物时。使用不含膦的铑催化剂，尤其是 4-甲氧基苯基乙烯配合物 7，反应进行快速定量，仅得到等摩尔量的相应 (E)-乙烯基硼烷 9 和 4-甲氧基乙基苯 8
• Hydrogen Release Studies of Alkali Metal Amidoboranes
  作者：Avery T. Luedtke、Tom Autrey

  DOI：10.1021/ic100119m

  日期：2010.4.19

  A series of metal amidoboranes LiNH2BH3 (LAB), NaNH2BH3 (SAB), LiNH(Me)BH3 (LMAB), NaNH(Me)BH3 (SMAB), KNH(Me)BH3 (PMAB), and KNH(Bu-t)BH3 (PBAB) were synthesized by solution phase methods, and the thermal release of H-2 in the solid state was studied. The mechanism of hydrogen release from metal amidoboranes, a metal ion assisted hydride transfer, is very different than the mechanism of hydrogen release from the parent compound ammonia borane (AB). On the basis of the observed trends in reaction rates of H > Me > Bu-t, K > Na > Li, and the kinetic isotope effect, the mechanism of hydrogen release from MAB compounds was found to proceed through a bimolecular mechanism involving the intermediacy of a MH (M = Li, Na, or K). The non-volatile products formed from MABs are significantly different than the products formed after hydrogen release from AB. The boron containing products resulting from the release of 1 equiv of hydrogen from the metal amidoboranes were characterized by MAS B-11 NMR spectroscopy and found to contain both BH3 and sp(2) hybridized BH groups, consistent with the general structure MN(R)=BHN(R)MBH3.
• Rotational dynamics in ammonia borane: Evidence of strong isotope effects
  作者：R. Cantelli、A. Paolone、O. Palumbo、F. Leardini、T. Autrey、A. Karkamkar、A.T. Luedtke

  DOI：10.1016/j.jallcom.2013.03.148

  日期：2013.12

  This work reports anelastic spectroscopy measurements on the partially deuterated (ND3BH3 and NH3BD3) and perdeuterated (ND3BD3) ammonia borane (NH3BH3) compounds. The relaxations previously reported in NH3BH3 are observed in all the samples, and are ascribed to the rotational and torsional dynamics of NH(D)(3)BH(D)(3) complexes.A new thermally activated peak appears at 70 K (for a vibration frequency of similar to 1 kHz) in the spectrum of NH3BD3 and ND3BD3. The peak is practically a single-time Debye process, indicating absence of interaction between the relaxing units, and has a strikingly high intensity. A secondary relaxation process is also detected around 55 K. The anelastic spectrum of the ND3BH3 only displays this less intense process at 55 K. The analysis of the peaks supplies information about the dynamics of the relaxing species, and the obtained results provide indications on the effect of partial and selective deuteration on the hydrogen (deuterium) dynamics. (C) 2013 Elsevier B.V. All rights reserved.
• Efficient Catalysis of Ammonia Borane Dehydrogenation
  作者：Melanie C. Denney、Vincent Pons、Travis J. Hebden、D. Michael Heinekey、Karen I. Goldberg

  DOI：10.1021/ja062419g

  日期：2006.9.1

  In the presence of an iridium pincer complex, dehydrogenation of ammonia borane (H3NBH3) occurs rapidly at room temperature in tetrahydrofuran to generate 1.0 equivalent of H2 and [NH2BH2]5. A metal borohydride complex has been isolated as a dormant form of the catalyst which can be reactivated by reaction with H2.