1,3-二甲基-1,3,2-二氮杂硼杂环戊烷 | 38151-26-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂环化合物
• 中文名称: 1,3-二甲基-1,3,2-二氮杂硼杂环戊烷
• 英文名称: 1,3-dimethyl-[1,3,2]diazaborolidine
• 英文别名: 1,3-dimethyl-1,3-diaza-2-boracyclopentane；1,3-dimethyl-1,3,2-diazaborolane；1,3-Dimethyl-1,3-diaza-2-borolidin；1,3-Dimethyl-1,3,2-diazaborolidin；1,3,2-Diazaborolidine, 1,3-dimethyl-；1,3-dimethyl-1,3,2-diazaborolidine
• CAS: 38151-26-7
• 化学式: C₄H₁₁BN₂
• 分子量: 97.9557
• InChiKey: AOWIQFUFOOJULP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.87
• 重原子数：
  7
• 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：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2901100000

反应信息

• 作为反应物：
  描述：

  1,5-已二烯 、 1,3-二甲基-1,3,2-二氮杂硼杂环戊烷 在 Sm(pentamethylcyclopentadienyl)2*THF 作用下， 以 甲苯 为溶剂， 反应 18.0h， 生成 2-Cyclopentylmethyl-1,3-dimethyl-[1,3,2]diazaborolidine
  参考文献：
  名称：

  1，5-和1，6-二烯的有机锡催化的环化/硼化。

  摘要：

  [图：见正文]在催化量的Cp * 2Sm.THF存在下，1,5-和1,6-二烯进行环化/硼化反应。可以使用标准条件将所得的有机硼烷氧化为相应的伯环醇。

  DOI：

  10.1021/ol006841s
• 作为产物：
  描述：

  在 Cp*₂ScCH₂SiMe₃ 作用下， 以 氘代苯 为溶剂， 反应 0.08h， 以95%的产率得到1,3-二甲基-1,3,2-二氮杂硼杂环戊烷
  参考文献：
  名称：

  Dehydrogenation of (Di)amine–Boranes by Highly Active Scandocene Alkyl Catalysts

  摘要：

  The scandocene alkyl complexes (C5Me5)(2)ScR (I, R = CH(SiMe3)(2); 5, R = CH2SiMe3) were found to be highly active catalysts for the dehydrogenation of dimethylamine borane (DMAB), exhibiting turnover frequencies up to 100 min(-1) ambient temperature. The beta-B-agostic scandium amidoborane intermediate 6 was isolated from a stoichiometric reaction of complex 5 with DMAB. In contrast, treatment of complex 5 with sterically bulky diisopropylamine-borane led to isolation of the aminoborane-coordinated scandocene hydride 7 via a complete beta-H elimination. Scandium amidoborane complex 6 showed scandium hydride like reactivity toward dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP), affording DCC insertion product 8 and DMAP ortho-borylation product 9, respectively. In addition, complexes 1 and 5 also showed remarkably high activity for the catalyzed dehydrogenative cyclization of diamine-boranes to give N-heterocyclic boranes.

  DOI：

  10.1021/acs.organomet.9b00461
• 作为试剂：
  描述：

  异己烯 在 bis(trimethylsilyl)azanide;[(Z)-N-ditert-butylphosphanyl-C-phenylcarbonimidoyl]-[2,6-di(propan-2-yl)phenyl]azanide;iron(2+) 、 1,3-二甲基-1,3,2-二氮杂硼杂环戊烷 作用下， 以 neat (no solvent) 为溶剂， 反应 18.0h， 生成 2-甲基-1-戊醇 、 4-甲基-1-戊醇
  参考文献：
  名称：

  钴和铁催化的异构化-支链烯烃的加氢硼化：品加烷硼烷和1,3,2-二氮杂硼烷的末端硼氢化

  摘要：

  The synthesis and characterization of a series of structurally varied N-phosphinoamidinate-ligated cobalt complexes is described, along with the successful application of these and a related iron complex as precatalysts in the isomerization hydroboration of terminal, geminal, and internal alkenes. These reactions proceed under mild conditions (23-65 degrees C), at relatively low base-metal loadings (1-5 mol %), typically without cosolvent, and with high terminal hydroboration selectivity across a broad spectrum of branched alkenes. With some of the alkene substrates examined, the Nphosphinoamidinate-ligated precatalysts employed herein are shown to provide alternative terminal selectivity versus other previously reported precatalyst classes for such transformations. Reports of terminal-selective metal-catalyzed alkene isomerization hydroboration disclosed thus far in the literature employ pinacolborane (HBPin); while effective in the system herein, we also report the first examples of such transformations employing either 1,3-dimethyl-1,3-diaza-2-boracydopentane or benzo-1,3,2-diazaborolane. The application of these 1,3,2-diazaborolanes in place of HBPin in some instances enables novel terminal selectivity in the isomerization hydroboration of branched alkenes.

  DOI：

  10.1021/acs.organomet.6b00823

文献信息

• A Highly Effective Ruthenium System for the Catalyzed Dehydrogenative Cyclization of Amine-Boranes to Cyclic Boranes under Mild Conditions
  作者：Christopher J. Wallis、Gilles Alcaraz、Alban S. Petit、Amalia I. Poblador-Bahamonde、Eric Clot、Christian Bijani、Laure Vendier、Sylviane Sabo-Etienne

  DOI：10.1002/chem.201501569

  日期：2015.9.7

  disclosed a new ruthenium‐catalyzed dehydrogenative cyclization process (CDC) of diamine–monoboranes leading to cyclic diaminoboranes. In the present study, the CDC reaction has been successfully extended to a larger number of diamine–monoboranes (4–7) and to one amine–borane alcohol precursor (8). The corresponding NB(H)N‐ and NB(H)O‐containing cyclic diaminoboranes (12–15) and oxazaborolidine (16) were

  我们最近披露了一种新的钌催化的二胺-单硼烷烷的脱氢环化过程（CDC），可形成环状的二氨基硼烷。在本研究中，CDC反应已经成功地扩展到二胺- monoboranes（更大数目的4 - 7）和一种胺-硼烷醇前体（8）。相应的NB（H）N-和NB（H）O含环状diaminoboranes（12 - 15）和恶唑硼烷（16）以高到高的产量获得。评估了起始胺-硼烷底物上的多种取代方式，并且还使用手性底物进行了反应。已经花了很多努力来了解钌CDC流程的机制。除了计算方法外，还对六碳链二胺一硼烷21进行了能够对导致NB（H）N键形成的催化过程的连续事件进行动力学区分的策略，并用15 N NMR研究。具有反应性NHMe末端的长寿命双-σ-硼烷钌中间体23进行了原位表征，并被证明可催化1的脱氢环化，确定双σ-硼烷钌配合物是CDC过程中的关键中间体。
• Dehydrogenation of Diamine-Monoboranes to Cyclic Diaminoboranes: Efficient Ruthenium-Catalyzed Dehydrogenative Cyclization
  作者：Christopher J. Wallis、Hellen Dyer、Laure Vendier、Gilles Alcaraz、Sylviane Sabo-Etienne

  DOI：10.1002/anie.201108874

  日期：2012.4.10

  Remote control: The title reaction is the first example of a catalyzed dehydrogenative cyclization (CDC) of diamine–monoboranes to give cyclic diaminoboranes. The cyclization reaction is strongly dependent on the nature of the substitution pattern at the remote amino group.

  远程控制：标题反应是二胺单硼烷催化脱氢环化（CDC）生成环状二氨基硼烷的第一个例子。环化反应很大程度上取决于在远端氨基处的取代模式的性质。
• Catalytic Dehydrogenation of (Di)Amine-Boranes with a Geometrically Constrained Phosphine-Borane Lewis Pair
  作者：Maxime Boudjelel、E. Daiann Sosa Carrizo、Sonia Mallet−Ladeira、Stéphane Massou、Karinne Miqueu、Ghenwa Bouhadir、Didier Bourissou

  DOI：10.1021/acscatal.8b00152

  日期：2018.5.4

  The o-phenylene bridged phosphine-borane iPr2P(o-C6H4)B(Fxyl)22 was prepared. Despite ring strain, it adopts a closed form, as substantiated by NMR, XRD, and DFT analyses. However, the corresponding open form is only slightly higher in energy. The dormant Lewis pair 2 proved to efficiently catalyze the dehydrogenation of a variety of amine- and diamine-boranes under mild conditions. The corresponding

  制备邻苯撑桥连的膦-硼烷i Pr 2 P（o -C 6 H 4）B（己基）2 2。尽管有环应变，但仍采用密闭形式，通过NMR，XRD和DFT分析证实。但是，相应的开放形式在能量上仅稍高一些。休眠的路易斯对2被证明可以在温和的条件下有效催化多种胺和二胺-硼烷的脱氢反应。相应的硼酸i i Pr 2 PH（o -C 6 H 4）BH（Fxyl）2 3被鉴定为这些脱氢反应的关键中间体。3释放H 2的倾向在催化周转中起主要作用。
• Boronnitrogen compounds
  作者：Wilhelm Weber、Kurt Niedenzu

  DOI：10.1016/s0022-328x(00)81470-9

  日期：1981.2

  New monomeric N-borylated pyrazole and imidazole derivatives have been synthesized and some of their characteristic features have been explored. The suggested structures are supported by spectroscopic data.

  合成了新的单体N-硼化的吡唑和咪唑衍生物，并探索了它们的一些特征。建议的结构由光谱数据支持。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: B-Verb.1, 2.5.1.3, page 122 - 126
  作者：

  DOI：——

  日期：——

表征谱图