1-(2'-picolyl)-ortho-carborane | 208348-94-1

• 英文名称: 1-(2'-picolyl)-ortho-carborane
• 英文别名: 1-(2'-picolyl)-o-carborane；closo-1-(2-NC5H4)(CH2)-1,2-C2B10H11
• CAS: 208348-94-1
• 化学式: C₈H₁₇B₁₀N
• 分子量: 235.34
• InChiKey: PNUABITVJYBNPA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1-(2'-picolyl)-ortho-carborane 在 potassium hydroxide 、 CO₂ 作用下， 以 乙醇 为溶剂， 以99%的产率得到[nido-7-HNC5H4(CH2)-7,8-C2B9H11]
  参考文献：
  名称：

  Synthesis of Ortho- and Meta-Re(I)-Metallocarboranes in Water

  摘要：

  A series of metallocarboranes of the types rac[M(CO)(3)(n(5)-7-R-7,8-C2B9H11)](-)and rac-[M(CO)(3)(n(5)-7-R-8-R'-7,8-C2B9H11)](-), and rac-[M(CO)(3)(n(5)-7-R-7,9-C2B9H11)](-) (M = Re) were prepared by reacting [NEt4](2)[Re(CO)(3)Br-3] or [Re(CO)(3-)(OH2)(3)]Br with the corresponding carboranes in the presence of aqueous solutions of either alkali metal or tetraalkylammonium fluoride salts. Carborane derivatives that were investigated included those containing pyridine, amino, carboxylic acid, carbohydrate, and aryl substituents, During the course of the research, it was discovered that Re metallocarboranes can be prepared directly from the respective closo-clusters under similar reaction conditions used with nido-carboranes. Reaction yields ranged from modest to excellent depending on the carborane isomer and the nature of the cage substituent(s). A crystal structure of an amine-substituted Re metal locarborane was obtained where the complex crystallized in the orthorhombic space group P2(1)2(1)2(1) with a = 8.982(2) angstrom, b 11.563(3) angstrom, c = 16.811(4) angstrom, (alpha = beta = gamma = 90 degrees, V = 1746.1(7) angstrom(3), Z = 4, and R1 = 0.0684.

  DOI：

  10.1021/ic0511221
• 作为产物：
  描述：

  2-氯甲基吡啶 、 1,2-dicarba-closo-dodecaborane(12) 在 BuLi 作用下， 以 乙醚 、 正己烷 为溶剂， 以57%的产率得到1-(2'-picolyl)-ortho-carborane
  参考文献：
  名称：

  Intra- and inter-molecular carboranyl C–H⋯N hydrogen bonds in pyridyl-containing ortho-carboranesElectronic supplementary information (ESI) available: rotatable 3-D molecular structure diagrams of experimental structures of 1–4 and of MP2/6-31G* optimised geometries 1a–7b in CHIME format. Computed GIAO NMR data for 1b–4c. See http://www.rsc.org/suppdata/dt/b2/b209931d/

  摘要：

  我们采用标准程序的改良方法制备了 1-R-1,2-C2B10H11 四种 C 取代的正硼烷衍生物，其中 R = 2â²-吡啶基 (1)、2â²-吡啶基 (2)、5â²-溴-2â²-吡啶基 (3) 或 3â²-吡啶基 (4)，并通过单晶 X 射线衍射研究对其进行了结构表征，以探索涉及硼烷 CH 单元的 CâHâ¯N 氢键效应。在 MP2/6-31G* 理论水平上进行的计算用于评估检测到的氢键强度，在 GIAO-B3LYP/6-311G* 水平上进行的核磁共振位移计算与测量到的 CâH 位移进行了比较，结果表明，在化合物 1 的情况下，分子内 CâHâ¯N 氢键在溶液中持续存在。 此外，还研究了红外 CâH 伸展频率在这些体系中探测氢键的价值。此外，还介绍了将化合物 3 转化为大环化合物 (C2B10H10C5H3N)3 的一次失败尝试，在该大环化合物中，三个正硼烷单元通过 2,5 二甲基吡啶环相连。

  DOI：

  10.1039/b209931d

文献信息

• Synthesis, characterization, and reactivity of new types of constrained geometry group 4 metal complexes derived from picolyl-substituted dicarbollide ligand systems
  作者：Jong-Dae Lee、Young-Joo Lee、Ki-Chul Son、Won-Sik Han、Minserk Cheong、Jaejung Ko、Sang Ook Kang

  DOI：10.1016/j.jorganchem.2007.08.027

  日期：2007.11

  The syntheses of group 4 metal complexes containing the picolyldicarbollyl ligand DcabPyH [nido-7-HNC5H4(CH2)-8-R-7,8-C2B9H10] (2) are reported. New types of constrained geometry group 4 metal complexes (DcabPy)MCl2, [(η5-RC2B9H9)(CH2)(η1-NC5H4)}MCl2] (M = Ti, 3; Zr, 4; R = H, a; Me, b), were prepared by the reaction of 2 with M(NMe2)2Cl2 (M = Ti, Zr). The reaction of 2 with M(NMe2)4 in toluene afforded

  据报道，合成了含有甲基吡啶基二咔唑基配体DCAB Py H [ nido -7-HNC 5 H 4（CH 2）-8-R-7,8-C 2 B 9 H 10 ]（2）的第4组金属配合物。新类型的几何受限4族金属配合物（DCAB PY）的MC1 2，[（η 5 -RC 2乙9 ħ 9）（CH 2）（η 1 -NC 5 H ^ 4）}的MC1 2 ]（M =钛，3 ; Zr，4; R = H，a ; Me，b），是通过2与M（NMe 2）2 Cl 2（M = Ti，Zr）反应制备的。反应2其中M（NME 2）4在甲苯中，得到（DCAB PY）M（NME 2）2，[（η 5 -RC 2乙9 ħ 9）（CH 2）（η 1 -NC 5 H ^ 4）} M（NMe 2）2 ]（M = Ti，5 ; Zr，6 ; R = H，一个; Me，b），其易于与Me 3 SiCl反应生成相应的氯化物络合物（DCAB
• Preparation, Structure, and Olefin Polymerization Behavior of a Picolyl-Functionalized Carborane Nickel(II) Complex
  作者：Xin Wang、Guo-Xin Jin

  DOI：10.1021/om0493356

  日期：2004.12.1

  X-ray structure analysis was performed on the complex, where the potential C,N-chelate ligand 1 was found to coordinate in a bidentate mode. The carborane complex 2 shows moderate catalytic activities of up to 3 × 106 g of PNB (mol of Ni)-1 h-1 for the addition polymerization of norbornene in the presence of methylaluminoxane (MAO) as cocatalyst. Catalytic activities, molecular weights, and molecular weight

  由单硼烷碳硼烷LiHC 2 B 10 H 10（= LiCab）和甲基吡啶氯制备了由甲基吡啶基官能化的邻碳硼烷配体Cab N H（1 ; Cab N H = 1-（2'- picolyl）-o - carborane） （2-CH 2 ClC 5 H 5 N）。1用n-BuLi锂化，然后与Ni（PPh 3）2 Cl 2反应，得到单核Ni络合物[（Cab N）2 ] Ni（2）。2个通过IR和NMR光谱及元素分析表征。另外，对复合物进行X射线结构分析，其中发现潜在的C，N-螯合配体1以双齿模式配位。碳硼烷配合物2只显示了中度的高达3×10的催化活性6克PNB的（镍摩尔）- 1个H ^ - 1为降冰片烯的甲基铝氧烷中的（MAO）的存在下，加成聚合作为助催化剂。聚降冰片烯（PNB）的催化活性，分子量和分子量分布已在各种反应条件下进行了研究。
• Iridium-catalyzed regioselective B(3,6)-dialkenylation or B(4)-alkenylation of <i>o</i>-carboranes <i>via</i> B–H activation and 1,2-carbon migration of alkynes
  作者：Huifang Zhang、Ruofei Cheng、Zaozao Qiu、Zuowei Xie

  DOI：10.1039/d2cc05890a

  日期：——

  An efficient and highly selective Ir-catalyzed cage boron alkenylation of o-carboranes with diarylacetylenes coupled with 1,2-aryl migration has been developed, leading to B–H geminal addition products via vinylidene rearrangement.

  一种高效且高选择性的铱催化的笼状硼烯烃化反应已经发展，该反应使用二芳基乙炔与o-碳硼烷偶联，并伴随着1,2-芳基迁移，导致B-H同位素加成产物通过乙烯基重排反应。
• Palladium-Catalyzed Regioselective B(3,5)-Dialkenylation and B(4)-Alkenylation of <i>o</i>-Carboranes
  作者：Shasha Yuan、Huifang Zhang、Zaozao Qiu、Zuowei Xie

  DOI：10.1021/acs.joc.3c02496

  日期：2024.2.16

  Picolyl group directed B(3,5)-dialkenylation and B(4)-monoalkenylation of o-carboranes has been developed with a very low palladium catalyst loading. The degree of substitution is determined by the cage C(2)-substituents due to steric reasons. On the basis of experimental results, a plausible mechanism is proposed including electrophilic palladation and alkyne insertion followed by protonation.

  邻碳硼烷的 Picolyl 基定向 B（3,5）-二烯基化和 B（4）-单烯基化已经开发出来，具有非常低的钯催化剂负载。由于空间原因，取代程度由笼 C（2） 取代基决定。根据实验结果，提出了一种合理的机制，包括亲电钝化和炔烃插入，然后是质子化。
• Breaking the Base Barrier: Cu(II)-Mediated C–H Heteroarylation of o-Carboranes with Base-Sensitive Heteroaryl Halides
  作者：Mengfan Sun、Leijun Feng、Ju-You Lu

  DOI：10.1021/acs.orglett.4c00489

  日期：2024.5.10

  C-arylation reactions using strong bases are among the most frequently used transformations in carborane chemistry, there has been no general solution to allow for the use of weak bases in the reaction. Moreover, base-metal-promoted C–H heteroarylation with base-sensitive heteroaryl halides remained elusive. Herein, copper-mediated cage C–H (hetero)arylation has been achieved without the need for strong bases

  虽然使用强碱的笼式 C-芳基化反应是碳硼烷化学中最常用的转化反应之一，但还没有允许在反应中使用弱碱的通用解决方案。此外，碱金属促进的与碱敏感的杂芳基卤化物的C-H杂芳基化仍然难以捉摸。在此，无需强碱即可实现铜介导的笼式C-H（杂）芳基化，从而可以在广泛的底物范围内轻松合成各种C-（杂）芳基化碳硼烷，收率良好至优异和良好的官能团相容性。