tris(methoxybenzyl)proazaphosphatrane | 1267779-24-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: tris(methoxybenzyl)proazaphosphatrane
• 英文别名: 2,8,9-Tris[(4-methoxyphenyl)methyl]-2,5,8,9-tetraza-1-phosphabicyclo[3.3.3]undecane；2,8,9-tris[(4-methoxyphenyl)methyl]-2,5,8,9-tetraza-1-phosphabicyclo[3.3.3]undecane
• CAS: 1267779-24-7
• 化学式: C₃₀H₃₉N₄O₃P
• 分子量: 534.638
• InChiKey: CARXOVNNNUMSER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  38
• 可旋转键数：
  9
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  tris(methoxybenzyl)proazaphosphatrane 在 2,8,9-三甲基-2,5,8,9-四氮杂-1-磷双环(3,3,3)十一烷 作用下， 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Superbases in Confined Space: Control of the Basicity and Reactivity of the Proton Transfer

  摘要：

  Endohedral functionalization of the molecular cavity of host molecules is in high demand in many areas of supramolecular chemistry. When highly reactive species are incarcerated in the confined space of a molecular cavity, deep changes of their chemical properties are expected. Here, we show that the superbasic properties of proazaphosphatranes can be improved in the confined space of the molecular cavity of hemicryptophane hosts. A general and modular procedure is described to prepare supramolecular superbases with various cavity sizes. The rate of proton transfer is strongly dependent on the shape and size of the inner cavity of the designed superbasic structure. Kinetic and thermodynamic data are strongly correlated to the space available around the basic center as revealed by the X-ray molecular structures analyses.

  DOI：

  10.1021/ja409444s
• 作为产物：
  描述：

  4-甲氧基苯乙醛 在 potassium tert-butylate 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 7.0h， 生成 tris(methoxybenzyl)proazaphosphatrane
  参考文献：
  名称：

  The Chloroazaphosphatrane Motif for Halogen Bonding in Solution

  摘要：

  DOI：

  10.1021/acs.inorgchem.1c01005
• 作为试剂：
  描述：

  三甲基氰硅烷 、 4-methyl-N-(1-phenylethylidene)benzenesulfonamide 在 tris(methoxybenzyl)proazaphosphatrane 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以93%的产率得到N-(1-cyano-1-phenylethyl)-4-methylbenzenesulfonamide
  参考文献：
  名称：

  Verkade的Superbase作为Strecker反应的有机催化剂

  摘要：

  发现Verkade的超强碱是Strecker反应的有效有机催化剂，可在短的反应时间内获得高收率，并要求催化剂用量低。

  DOI：

  10.1002/ejoc.201801170

文献信息

• Endohedral Functionalized Cage as a Tool to Create Frustrated Lewis Pairs
  作者：Jian Yang、Bastien Chatelet、Véronique Dufaud、Damien Hérault、Sabine Michaud-Chevallier、Vincent Robert、Jean-Pierre Dutasta、Alexandre Martinez

  DOI：10.1002/anie.201808291

  日期：2018.10.22

  frustrated Lewis pair (FLP) system was obtained by confinement of the Lewis base partner, a Verkade's superbase, in a molecular cavity. Whereas the model superbase lacking cavity displayed no catalytic activity in Morita–Baylis–Hillman (MBH) reactions, when associated to titanium (IV) chloride, the encaged superbase turns out to be an efficient catalyst under the same conditions. The crucial role of the

  通过将路易斯碱伴侣（Verkade的超碱）限制在分子腔中来获得沮丧的路易斯对（FLP）系统。缺少空腔的模型超碱在Morita-Baylis-Hillman（MBH）反应中没有显示催化活性，而与氯化钛（IV）结合时，在相同条件下，包封的超碱却是一种有效的催化剂。内在功能化笼子对催化性能的关键作用还通过以下事实得到了证明：具有庞大取代基的模型超强碱生产活性催化剂的效率要低得多，以及通过抑制和底物选择实验。31P NMR光谱和质谱实验证明，当超碱被环戊撑碳烯（CTV）单元封端时，路易斯酸性和碱性配偶体之间没有发生相互作用，从而创建了真正的FLP活性体系。
• A New Step Towards Solid Base Catalysis: Azidoproazaphosphatranes Immobilized in Nanopores of Mesoporous Silica
  作者：Pascal Dimitrov Raytchev、Anissa Bendjeriou、Jean-Pierre Dutasta、Alexandre Martinez、Véronique Dufaud

  DOI：10.1002/adsc.201100270

  日期：2011.8

  proazaphosphatranes, known as Verkade’s superbases, were prepared for the first time by covalent immobilization onto SBA-15 silica. In order to introduce the tether to the surface, three siloxane-containing azido derivatives of the proazaphosphatranes were first synthesized (2a–c) which after post-synthetic grafting onto silica support led to the formation of hybrid materials of different basicity and steric properties

  通过共价键固定在SBA-15二氧化硅上，首次制备了由原氮杂磷杂环戊烷衍生而来的非均相碱性催化剂，即Verkade的超强碱。为了将系链引入表面，首先合成了三氮杂原磷烷的含硅氧烷叠氮基衍生物（2a–c），将其合成后接枝到二氧化硅载体上后，形成了具有不同碱性和空间特性的杂化材料，2a–c @ SBA-15。后者使用多种分子和固态技术进行了充分表征，以确定它们的结构和质地特性。然后，在蒽酮和3-羟基-2-吡喃酮与两种缺电子的亲二烯体的Diels–Alder反应中评估了这些新型的固体碱催化剂，N-甲基马来酰亚胺和富马酸二甲酯。通常，取决于催化剂的种类，可以获得高活性和选择性，其性能以甲氧基苄基>新戊基>甲基叠氮基磷杂环戊烯的顺序降低。研究了最好的催化剂，即甲氧基苄基衍生物2c @ SBA-15的催化剂循环利用，结果表明该催化剂可以重复使用多达3个循环，然后才能检测到任何活性降低。
• Synthesis of Gold(I) Complexes Bearing Verkade's Superbases
  作者：Bastien Chatelet、Paola Nava、Herve Clavier、Alexandre Martinez

  DOI：10.1002/ejic.201700897

  日期：2017.10.10

  investigated as ligands for gold(I). If the coordination to the gold center by the phosphorus atom suggests phosphine‐like behavior, gold(I)‐containing Verkade's superbase complexes could also be prepared from the weak conjugate acid azaphosphatrane by the formation of the corresponding silver complex and subsequent transmetalation to gold, similarly to the synthetic route used for complexes bearing N‐heterocyclic

  Proazaphosphatranes，也称为 Verkade 的超碱，已被研究作为金 (I) 的配体。如果磷原子与金中心的配位表明类似膦的行为，则含金 (I) 的 Verkade 超碱配合物也可以通过形成相应的银配合物并随后金属转移为金，由弱共轭酸氮杂磷烷制备，类似于用于带有 N-杂环卡宾配体 (NHC) 的配合物的合成路线。与 NHC 相比，竞争性转移金属实验强调了 Verkade 的超级碱的不稳定性更高。此外，理论和实验相结合的研究表明，它们显示出强大的 σ 供体能力，优于膦并且与 NHC 相似。因此，
• Encaging the Verkade’s Superbases: Thermodynamic and Kinetic Consequences
  作者：Pascal Dimitrov Raytchev、Alexandre Martinez、Heinz Gornitzka、Jean-Pierre Dutasta

  DOI：10.1021/ja1110333

  日期：2011.2.23

  Proazaphosphatranes, also known as Verkade's superbases, are nonionic species, which exhibit catalytic properties for a wide range of reactions. The properly designed host molecule 3 and its protonated counterpart [3 center dot H]Cl-+(-) were synthesized to study how confinement can modify the stability and the reactivity of a Verkade's superbase. The results show that the encapsulation does not alter the strong basicity of the proazaphosphatrane, but dramatically decreases the rate of proton transfer.
• Homogeneous and silica-supported azidoproazaphosphatranes as efficient catalysts for the synthesis of substituted coumarins
  作者：Pascal Dimitrov Raytchev、Lyvie Roussi、Jean-Pierre Dutasta、Alexandre Martinez、Véronique Dufaud

  DOI：10.1016/j.catcom.2012.07.012

  日期：2012.11

  Homogeneous and silica-supported azidoproazaphosphatranes derived from the Verkade's superbase catalyze the synthesis of substituted coumarins with moderate to good yields and high selectivity. (C) 2012 Elsevier B.V. All rights reserved.