4,4,11,11-tetramethyl-6,9-dioxa-1,3-diazatricyclo[6.3.0.0^3,7]undeca-7-ene-2-onium trifluoromethanesulfonate | 814254-77-8

• 英文名称: 4,4,11,11-tetramethyl-6,9-dioxa-1,3-diazatricyclo[6.3.0.0^3,7]undeca-7-ene-2-onium trifluoromethanesulfonate
• 英文别名: IBioxMe₄-OTf；IBioxMe4*HOTf；IBiox(Me)4.HOTf；5,5,9,9-tetramethyl-3,11-dioxa-8-aza-6-azoniatricyclo[6.3.0.02,6]undeca-1,6-diene;trifluoromethanesulfonate
• CAS: 814254-77-8
• 化学式: CF₃O₃S*C₁₁H₁₇N₂O₂
• 分子量: 358.339
• InChiKey: OBBUOEVEJFJTEX-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.08
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  92.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4,4,11,11-tetramethyl-6,9-dioxa-1,3-diazatricyclo[6.3.0.0^3,7]undeca-7-ene-2-onium trifluoromethanesulfonate 在 potassium carbonate 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  Simple synthetic access to [Au(IBiox)Cl] complexes

  摘要：

  报告了手性和非手性金-IBiox 复合物的绿色和可持续获取途径。根据 XRD 数据首次计算出了金-二氧化铀复合物的 %Vbur 。在苯乙炔的氢化反应中检验了它们的催化活性。

  DOI：

  10.1039/d3dt01357j
• 作为产物：
  描述：

  特戊酸氯甲酯 、 silver trifluoromethanesulfonate 、 4,5-dihydro-2-(4,5-dihydro-4,4-dimethyloxazol-2-yl)-4,4-dimethyloxazole 以 二氯甲烷 为溶剂， 反应 20.75h， 以83%的产率得到4,4,11,11-tetramethyl-6,9-dioxa-1,3-diazatricyclo[6.3.0.0^3,7]undeca-7-ene-2-onium trifluoromethanesulfonate
  参考文献：
  名称：

  空间要求高、生物恶唑啉衍生的 N-杂环卡宾配体具有有限的催化灵活性

  摘要：

  描述了从生物恶唑啉 (IBiox) 衍生的一个独特的 N-杂环卡宾家族，适用于过渡金属催化。配体富含电子，空间要求高，灵活性有限。它们的有用性已在空间位阻芳基氯化物和硼酸的 Suzuki-Miyaura 交叉偶联中得到证明。首次使用 Suzuki-Miyaura 方法从芳基氯合成了具有甲基和更大邻位取代基的四邻位取代联芳基化合物。

  DOI：

  10.1021/ja045349r
• 作为试剂：
  描述：

  (+/-)-N-(2-bromophenyl)-N-methyl-2-phenylpropamide 在 bis[chloro(1,2,3-trihapto-allylbenzene)palladium(II)] 、 caesium carbonate 、 cesium pivalate 、 4,4,11,11-tetramethyl-6,9-dioxa-1,3-diazatricyclo[6.3.0.0^3,7]undeca-7-ene-2-onium trifluoromethanesulfonate 作用下， 反应 18.0h， 生成 1,3-Dimethyl-3-phenylindol-2-one
  参考文献：
  名称：

  Remote Construction of N‐Heterocycles via 1,4‐Palladium Shift‐Mediated Double C−H Activation

  摘要：

  AbstractIn the past years, Pd0‐catalyzed C(sp3)−H activation provided efficient and step‐economical methods to synthesize carbo‐ and heterocycles via direct C(sp2)−C(sp3) bond formation. We report herein that a 1,4‐Pd shift allows access to N‐heterocycles which are difficult to build via a direct reaction. It is shown thato‐bromo‐N‐methylanilines undergo a 1,4‐Pd shift at theN‐methyl group, followed by intramolecular trapping by C(sp2)−H or C(sp3)−H activation at another nitrogen substituent and remote C−C bond formation to generate biologically relevant isoindolines and β‐lactams. The product selectivity is influenced by the employed ligand, with NHCs favoring the product of remote C−C coupling against products arising from direct C−C coupling and N‐demethylation.

  DOI：

  10.1002/anie.202116101

文献信息

• Rhodium(I) Complexes of the Conformationally Rigid IBioxMe₄ Ligand: Preparation of Mono-, Bis-, and Tris-ligated NHC Complexes
  作者：Adrian B. Chaplin

  DOI：10.1021/om500332n

  日期：2014.6.23

  The preparation and characterization of a series of mono-, bis-, and tris-ligated rhodium(I) complexes of Glorius’ conformationally rigid bioxazoline-derived N-heterocyclic carbene ligand IBioxMe4 are described. Through reaction of [Rh(COE)2Cl]2 (COE = cis-cyclooctene) with isolated IBioxMe4, [Rh(IBioxMe4)(COE)Cl]2 (1), trans-[Rh(IBioxMe4)2(COE)Cl] (2), and [Rh(IBioxMe4)3Cl] (3) were each isolated

  制备和一系列单- ，双-的表征，和Glorius的三配位的铑（I）配合物构象刚性bioxazoline衍生的N-杂环卡宾配体IBioxMe 4中描述。通过的反应的[Rh（COE）2 CL] 2（COE =顺-cyclooctene）与分离IBioxMe 4，铑[Rh（IBioxMe 4）（COE）CL] 2（1），反式- [铑（IBioxMe 4）2（ COE）CL]（2），和铑[Rh（IBioxMe 4）3 CL]（3）各自通过的反应条件的仔细的选择分离。的进一步取代和盐复分解反应1 - 3进行了调查含有，及其衍生物CO，降冰片二烯，以及环戊二烯基的辅助配体被容易地分离。值得注意的是，从卤化物抽象2和3使用Na [巴˚F 4 ]（AR ˚F = 3,5--C 6 H ^ 3（CF 3）2）导致形成低坐标T形顺- [铑（IBioxMe 4）2（COE）] [巴˚F 4 ]（9）和铑[Rh（IBioxMe
• Preparation of NHC Borane Complexes by Lewis Base Exchange with Amine− and Phosphine−Boranes
  作者：Malika Makhlouf Brahmi、Julien Monot、Marine Desage-El Murr、Dennis P. Curran、Louis Fensterbank、Emmanuel Lacôte、Max Malacria

  DOI：10.1021/jo101301d

  日期：2010.10.15

  A versatile new method for the preparation of NHC boranes starting from two stable, readily available reactants―an heterocyclic salt and an amine or phosphine−borane―is reported. It uses a Lewis base exchange at boron and provides easy access to new NHC boranes, in particular B-substituted borane ones.

  报道了一种从两种稳定的，易于获得的反应物-杂环盐和胺或膦-硼烷开始制备NHC硼烷的通用新方法。它在硼上使用路易斯碱交换，并易于获得新的NHC硼烷，特别是B取代的硼烷硼烷。
• Steric Effects in the Aerobic Oxidation of π-Allylnickel(II) Complexes with <i>N</i>-Heterocyclic Carbenes
  作者：Benjamin R. Dible、Matthew S. Sigman

  DOI：10.1021/ic0612451

  日期：2006.10.1

  Pi-allylchloro(NHC)nickel(II) complexes were synthesized and their reactions with O2 were studied. Ligand steric effects were found to determine the difference between rapid oxidation of the allyl group to produce bis-mu-hydroxonickel complexes and no observable reaction. The ability of the metal-NHC bond to rotate correlates with the ability of the complex to react with O2. In the limiting cases,

  合成了对烯丙基氯（NHC）镍（II）配合物，并研究了其与O2的反应。发现配体的空间效应确定了烯丙基的快速氧化以产生双-mu-羟基酮络合物与没有可观察到的反应之间的差异。金属-NHC键旋转的能力与配合物与O2反应的能力相关。在极限情况下，构象受限的配合物对O2稳定，且Ni-NHC键快速旋转的配合物与O2迅速反应。发现具有中间构象柔韧性的复合物与O 2的反应性较低。基于观察到的鞍形配体对O2的配合物的惰性，我们建议在与O2反应时采用非平面几何形状。
• Estimated Rate Constants for Hydrogen Abstraction from N-Heterocyclic Carbene−Borane Complexes by an Alkyl Radical
  作者：Andrey Solovyev、Shau-Hua Ueng、Julien Monot、Louis Fensterbank、Max Malacria、Emmanuel Lacôte、Dennis P. Curran

  DOI：10.1021/ol101014q

  日期：2010.7.2

  Rate constants for hydrogen abstraction by a nonyl radical from 20 complexes of N-heterocyclic carbenes and boranes (NHC−boranes) have been determined by the pyridine-2-thioneoxycarbonyl (PTOC) competition kinetic method at a single concentration point. The rate constants range from <1 × 104 to 8 × 104 M−1 s−1. They show little dependence on the electronic properties of the carbene core, but there

  已经通过吡啶-2-硫代氧羰基（PTOC）竞争动力学方法在单个浓度点上确定了壬基从20种N-杂环卡宾和硼烷（NHC-硼烷）的络合物中提取氢的速率常数。速率常数的范围是从<1×10 4到8×10 4 M -1 s -1。它们几乎不依赖于卡宾核的电子性质，但是存在随着卡宾N取代基尺寸的减小而增加速率常数的趋势。已经鉴定出两种有希望的具有小的N取代基的新试剂（R = Me）。
• Molecular versus Ionic Structures in Adducts of GaX₃ with Monodentate Carbon-Based Ligands
  作者：Ahmad El-Hellani、Julien Monot、Régis Guillot、Christophe Bour、Vincent Gandon

  DOI：10.1021/ic302440g

  日期：2013.1.7

  A molecular donor-acceptor adduct has been isolated by the reaction of the N-heterocyclic carbene 1,3-dimethyl imidazol-2-ylidene (diMe-IMD) with GaCl3. In contrast, the structurally related, yet much more nucleophilic, 1,3-dimethyl-2-methylene-2,3-dihydro-1H-imidazole (diMe-MDI) gave rise to ion pairs of type [L2GaX2][GaX4], where X = Cl, Br, or I. With IBioxMe(4), a N-heterocyclic carbene that is more nucleophilic than diMe-IMD, the outcome of the reaction was dependent on the nature of the halide. Ionic 1:1 adducts between monodentate ligands and GaX3 salts have only one precedent in the literature. The peculiar behavior of carbon-based ligands was explained on the basis of their electronic properties and reaction kinetics.