H[tris((4,4-dimethyl-2-oxazolinyl)phenylborate)] | 1177320-23-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: H[tris((4,4-dimethyl-2-oxazolinyl)phenylborate)]
• 英文别名: hydrogen tris(4,4-dimethyl-2-oxazolinyl)phenylborate；hydrogen tris(4,4-dimethyl-2-oxazolinyl)borate；HToM；HTo(M)
• CAS: 1177320-23-8
• 化学式: C₂₁H₂₉BN₃O₃*H
• 分子量: 383.298
• InChiKey: VKVZHNQNXGDBCS-UHFFFAOYSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  2.69
• 重原子数：
  28.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  64.77
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  H[tris((4,4-dimethyl-2-oxazolinyl)phenylborate)] 以 癸烷 、 氘代甲苯 、 苯 为溶剂， 生成 tris(4,4-dimethyl-2-oxazolinyl)phenylborato(tert-butylperoxy)zinc
  参考文献：
  名称：

  Remarkably Robust Monomeric Alkylperoxyzinc Compounds from Tris(oxazolinyl)boratozinc Alkyls and O₂

  摘要：

  Metal alkylperoxides are remarkable, highly effective, yet often thermally unstable, oxidants that may react through a number of possible pathways including O-O homolytic cleavage, M-O homolytic cleavage, nucleophilic O-atom transfer, and electrophilic O-atom transfer. Here we describe a series of zinc alkyl compounds of the type To(M)ZnR (To(M) = tris(4,4-dimethyl-2-oxazolinyl)phenylborate; R = Et, n-C3H7, i-C3H7, t-Bu) that react with O-2 at 25 degrees C to form isolable monomeric alkylperoxides To(M)ZnOOR in quantitative yield. The series of zinc alkylperoxides is crystallographically characterized, and the structures show systematic variations in the Zn-O-O angle and O-O distances. The observed rate law for the reaction of To(M)ZnEt (2) and O-2 is consistent with a radical chain mechanism, where the rate-limiting S(H)2 step involves the interaction of (OOR)-O-center dot and To(M)ZnR. In contrast, To(M)ZnH and To(M)ZnMe are unchanged even to 120 degrees C under 100 psi of O-2 and in the presence of active radical chains (e.g., (OOEt)-O-center dot). This class of zinc alkylperoxides is unusually thermally robust, in that the compounds are unchanged after heating at 120 degrees C in solution for several days. Yet, these compounds are reactive as oxidants with phosphines. Additionally, an unusual alkylperoxy group transfer to organosilanes affords To(M)ZnH and ROOSiR3'.

  DOI：

  10.1021/ja303440n
• 作为产物：
  描述：

  lithium tris(4,4-dimethyl-2-oxazolinyl)phenylborate 在 silica gel 作用下， 以 正己烷 、 异丙醇 为溶剂， 以50%的产率得到H[tris((4,4-dimethyl-2-oxazolinyl)phenylborate)]
  参考文献：
  名称：

  A New Scorpionate Ligand: Tris(4,4-dimethyl-2-oxazolinyl)borate and Its Zirconium(IV) Complexes

  摘要：

  The first example of a new class of oxazoline-based scorpionate ligand, tris(4,4-dimethyl-2-oxazolinyl)phenyl borate, [To(M)](-), is prepared by reaction of 2-lithio-4,4-dimethyl-2-oxazolide and 0.3 equiv of dichlorophenylborane. The steric bulk of this ligand is greater than that of tris(3,5-Me-2-pyrazolyl)borate (Tp*), as quantified by comparison of solid angles of crystallographically characterized zirconium(IV) complexes.

  DOI：

  10.1021/om800252p

文献信息

• Divergent reaction pathways of tris(oxazolinyl)borato zinc and magnesium silyl compounds
  作者：Debabrata Mukherjee、Nicole L. Lampland、KaKing Yan、James F. Dunne、Arkady Ellern、Aaron D. Sadow

  DOI：10.1039/c2cc36953b

  日期：——

  Synthesis and reactivity of monomeric magnesium and zinc silyl compounds To(M)M-Si(SiHMe2)3 and To(M)M-Si(SiMe3)3 are described (To(M) = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The magnesium compounds react slowly with water and air, while the zinc compounds are inert. With CO2, To(M)Mg-Si(SiHMe2)3 provides To(M)MgO2CSi(SiHMe2)3 through CO2 insertion, whereas To(M)Zn-Si(SiHMe2)3 affords To(M)ZnOCHO

  描述了单体镁和锌甲硅烷基化合物To（M）M-Si（SiHMe2）3和To（M）M-Si（SiMe3）3的合成和反应性（To（M）= tris（4,4-dimethyldimethyl-2 -恶唑啉基）苯基硼酸酯）。镁化合物与水和空气缓慢反应，而锌化合物是惰性的。对于CO2，To（M）Mg-Si（SiHMe2）3通过插入 提供To（M）MgO2CSi（SiHMe2）3，而To（M）Zn-Si（SiHMe2）3提供To（M）ZnOCHO。
• Bis(oxazolinyl)phenylborane: A Lewis acid-containing ligand for methide abstraction-based coordination to aluminum(III)
  作者：James F. Dunne、Kuntal Manna、Jerzy W. Wiench、Arkady Ellern、Marek Pruski、Aaron D. Sadow

  DOI：10.1039/b911851a

  日期：——

  A compound that contains a Lewis acidic boron center and coordinating oxazoline groups, bis(4,4-dimethyl-2-oxazolinyl)phenylborane (PhB(OxMe2)2; 1), has been prepared and spectroscopically characterized. Solvent dependent 15N and 11B NMR spectroscopic properties and solid-state 11B NMR measurements provide support for intermolecular interactions involving Lewis acid and base sites. The bifunctional

  含有路易斯酸性的化合物 硼 中心和协调 恶唑啉 组， 双（4,4-二甲基-2-恶唑啉基）苯基硼烷 （PhB（Ox ME2）2; 1），已经制备并经光谱表征。溶剂依赖15 N和11 B NMR光谱性质以及固态11 B NMR测量为涉及路易斯酸和碱基的分子间相互作用提供了支持。的双功能性质恶唑啉基硼烷 1通过与（AlMe 3）2，通过 甲基化物 硼的抽象和 恶唑啉 协调 铝 产生[（κ 2 -PhMeB（OX ME2）2阿尔梅2 ]（2）。与相关化合物相比，化合物2包含一个平面六元螯合环双（吡唑基）硼铝起皱的化合物。此外，化合物2和相关的双齿三（恶唑啉基）苯基硼基二甲基铝 对...惰性 甲基铝键质子分解。这种强大的特性表明可以使用这些恶唑啉基硼铝 催化反应中的化合物 丙交酯 开环聚合。
• Ligand Exchange Reactions and Hydroamination with Tris(oxazolinyl)borato Yttrium Compounds
  作者：Andrew V. Pawlikowski、Arkady Ellern、Aaron D. Sadow

  DOI：10.1021/ic900689k

  日期：2009.8.17

  precatalysts for the cyclization of aminoalkenes; the kinetics of catalytic conversion indicate zero-order substrate dependence and first-order catalyst dependence. Kinetic investigations of ligand exchange processes and hydroamination reactions indicate that the tris(oxazolinyl)borato-yttrium interaction is robust even in the presence of excess phosphine oxide and primary and secondary amines.

  配位体取代反应和催化加氢胺化/ aminoalkenes的环化进行了研究用新oxazolinylborato钇化合物，三（4,4-二甲基-2-恶唑啉基）phenylborato双（三甲基硅甲基）钇（[Y（κ 3 -To中号）（CH 2 SiMe 3）2（THF）]，1）。1中的THF在室温下快速交换，并且通过模拟从190至280 K获得的1 H NMR光谱获得的活化参数与解离机理一致（ΔS ‡ = 30±1 eu，ΔG ‡ = 11.9 kcal mol -1在243 K）。相关膦乙烷加成物[Y（κ 3 -To中号）（CH 2森达3）2（OPPh 3）]（2）也经历经由OPPh交换3离解具有高得多的屏障（Δ ģ ‡ = 15.0千卡摩尔- 1在320 K）。化合物1与胺t BuNH 2，对-MeC 6 H 4 NH 2和2,6- i Pr 2 C 6 H 3 NH 2反应提供六坐标[Y（κ
• Concerted C−N and C−H Bond Formation in a Magnesium-Catalyzed Hydroamination
  作者：James F. Dunne、D. Bruce Fulton、Arkady Ellern、Aaron D. Sadow

  DOI：10.1021/ja108881s

  日期：2010.12.22

  tris(4,4-dimethyl-2-oxazolinyl)phenylborate) is an active precatalyst for intramolecular hydroamination/cyclization at 50 °C. The empirical rate law of -d[substrate]/dt = k'(obs)[Mg](1)[substrate](1) and Michaelis-Menten-type kinetics are consistent with a mechanism involving reversible catalyst-substrate association prior to cyclization. The resting state of the catalyst, To(M)MgNHCH(2)CR(2)CH(2)CH═CH(2)

  配位饱和 To(M)MgMe (1; To(M) = tris(4,4-二甲基-2-恶唑啉基)苯基硼酸酯)是一种在 50 °C 下分子内加氢胺化/环化的活性预催化剂。-d[底物]/dt = k'(obs)[Mg](1)[底物](1) 和 Michaelis-Menten 型动力学的经验速率定律与涉及可逆催化剂 - 底物结合之前的机制一致环化。催化剂的静止状态 To(M)MgNHCH(2)CR(2)CH(2)CH=CH(2) [R = Ph, Me, -(CH(2))(5)-] 是可分离但分离的镁酰氨基烯烃在 50 °C 下不会发生单分子环化。然而，添加痕量底物允许发生环化。因此，我们提出了一种包含协调的 CN 键形成和 NH 键裂解的两底物、六中心过渡态，作为催化循环的周转限制步骤。
• Development of a novel scorpionate ligand with 6-methylpyridine and comparison of the structural and electronic properties of nickel(<scp>ii</scp>) complexes with related tris(azolyl)borates
  作者：Yusuke Fujiwara、Tomoaki Takayama、Jun Nakazawa、Masaya Okamura、Shiro Hikichi

  DOI：10.1039/d2dt01548j

  日期：——

  A novel anionic tridentate borate ligand with a 6-methylpyridyl donor, TpyMe, has been synthesized. Comparison of the molecular structures and reactivities of nickel(II)-bromido complexes with tris(azolyl)borate ligands composed of pyridyl, pyrazolyl, or oxazolinyl donors indicates the characteristic sterically demanding nature and strong electron donating ability of TpyMe.

  已经合成了一种具有 6-甲基吡啶基供体 Tpy Me的新型阴离子三齿硼酸盐配体。比较镍( II )-溴化配合物与由吡啶基、吡唑基或恶唑啉基供体组成的三(唑基)硼酸盐配体的分子结构和反应性，表明Tpy Me具有独特的空间要求性质和强给电子能力。