(4-(dimethylamino)pyridine)·BPh₃ | 202059-36-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (4-(dimethylamino)pyridine)·BPh₃
• 英文别名: DMAP·BPh₃；DMAP-BPh₃；[4-(Dimethylamino)pyridin-1-ium-1-yl]-triphenylboranuide
• CAS: 202059-36-7
• 化学式: C₂₅H₂₅BN₂
• 分子量: 364.298
• InChiKey: DKTPDAXRLSMJEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.56
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  7.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4-二甲氨基吡啶 、 四苯硼钠 在 3-methyl-1,4-dioxane-2,5-dione 作用下， 以 苯 为溶剂， 以36%的产率得到(4-(dimethylamino)pyridine)·BPh₃
  参考文献：
  名称：

  衍生自乙交酯和丙交酯的18元环酯：制备，结构和与钠离子的配位。

  摘要：

  由乙交酯或丙交酯（4当量）与4-二甲氨基吡啶，DMAP（1当量）和NaBPh（4）（1当量）在苯中于70°C下反应制得的环状酯加合物（CH（2）C（O分别形成）（O）（6）NaBPh（4）和（CHMeC（O）O）（6）NaBPh（4）。Na [（S，R，S，R，S，R）-（CH（3）CHC（O）O）（6）]（2）BPh（4）.CH（3）CN和据报道（CH（2）C（O）O）（6）NaBPh（4）。（CH（3）CN）（2）。通过色谱分离环状酯和（CH（2）C（O）O）（6），（S，R，R，R，R，R）-（CHMeC（O）O）（6）的结构和（S，S，R，R，R，R）-（CHMeC（O）O）（6）被确定。报告了（CHMeC（O）O）（6）的六个对映异构体之一和两个内消旋异构体的（1）H和（13）C NMR数据。根据DMAP和NaBPh（4）在产生NaPh和DMAP的热苯中的初始反应，讨论了形成这些

  DOI：

  10.1039/b709081a

文献信息

• Reactive Dimerization of an N-Heterocyclic Plumbylene: C−H Activation with Pb^II
  作者：Robin Guthardt、Jan Oetzel、Julia I. Schweizer、Clemens Bruhn、Robert Langer、Martin Maurer、Jan Vícha、Pavletta Shestakova、Max C. Holthausen、Ulrich Siemeling

  DOI：10.1002/anie.201811559

  日期：2019.1.28

  The N‐heterocyclic plumbylene [Fe(η5‐C5H4)NSiMe3}2Pb:] is in equilibrium with an unprecedented dimer in solution, whose formation involves the cleavage of a strong C−H bond and concomitant formation of a Pb−C and an N−H bond. According to a mechanistic DFT assessment, dimer formation does not involve direct PbII insertion into a cyclopentadienyl C−H bond, but is best described as an electrophilic

  N-杂环plumbylene的[Fe （η 5 -C 5 H ^ 4）NSiMe 3 } 2铅：]处于平衡与溶液中前所未有的二聚体，其形成包括强C-H键和的伴随形成的切割Pb-C和N-H键。根据机械DFT评估，二聚体的形成不涉及直接将Pb II插入环戊二烯基CH键中，而最好描述为亲电取代。笨重plumbylene的[Fe （η 5 -C 5 H ^ 4）NSitBuMe 2 } 2Pb：]没有显示二聚作用，但通过形成分子内Fe-Pb键来补偿其亲电性。
• Iron-catalysed ring-opening metathesis polymerization of olefins and mechanistic studies
  作者：Satoshi Takebayashi、Mark A. Iron、Moran Feller、Orestes Rivada-Wheelaghan、Gregory Leitus、Yael Diskin-Posner、Linda J. W. Shimon、Liat Avram、Raanan Carmieli、Sharon G. Wolf、Ilit Cohen-Ofri、Rajashekharayya A. Sanguramath、Roy Shenhar、Moris Eisen、David Milstein

  DOI：10.1038/s41929-022-00793-4

  日期：——

  discovery and mechanistic studies of three-coordinate iron(II) catalysts for ring-opening metathesis polymerization of olefins. Remarkably, their reactivity enabled the formation of polynorbornene with stereoregularity and high molecular weight (>107 g mol–1). The polymerization in the presence of styrene revealed cross metathesis reactivity with iron catalysts. Mechanistic studies suggest the possible

  烯烃复分解反应是碳-碳双键形成中应用最广泛的催化反应之一。目前，Mo-和Ru-卡宾催化剂是该反应最常见的选择。有人提出，铁基催化剂将是 Ru 催化剂的理想经济和生物相容性替代品；然而，仍然缺乏这方面的实际解决办法。在这里，我们报告了用于烯烃开环复分解聚合的三配位铁 (II) 催化剂的发现和机理研究。值得注意的是，它们的反应性使得能够形成具有立体规整性和高分子量 (>10 7  g mol –1 ) 的聚降冰片烯）。在苯乙烯存在下的聚合揭示了与铁催化剂的交叉复分解反应。机理研究表明金属-配体合作在生产催化剂的形成中可能发挥的作用。这项工作为开发铁络合物打开了大门，铁络合物可以成为烯烃复分解反应的经济且生物相容的催化剂。
• (η³-α-Silabenzyl)tungsten Complexes: An Isolable Intermediate for Interconversion between a Silylene Complex and a Silyl Complex through 1,2-Aryl Migration
  作者：Eiji Suzuki、Takashi Komuro、Yuto Kanno、Hiromi Tobita

  DOI：10.1021/om4000105

  日期：2013.2.11

  eta(3)-alpha-Silabenzyl complexes Cp*W - (CO)(2)eta(3)(Si,C,C)-Si(p-Tol)(2)R} (1a, R = Me; 1b, R = p-Tol; Cp* = eta(5)-C5Me5, p-Tol = p-tolyl), the first silicon analogues of eta(3)-benzyl complexes, were synthesized by abstraction of DMAP (4-(dimethylamino)pyridine) with BPh3 either from (aryl)(DMAP.silylene)tungsten complexes 2a,b at room temperature or from (arylsilyl)(DMAP)tungsten complexes 3a,b under irradiation. Complex I was demonstrated to be a key intermediate for the interconversion between 2 and 3 and to serve as a synthetic equivalent for both base-free silylene complexes and coordinatively unsaturated silyl complexes.
• Reactions of Tungsten Acetylide–Silylene Complexes with Pyridines: Direct Observation of Silylene/Silyl Migration in Tungsten Acetylide and Carbyne/Vinylidene Frameworks
  作者：Hiroyuki Sakaba、Hiroyuki Oike、Yasuhiro Arai、Eunsang Kwon

  DOI：10.1021/om300772c

  日期：2012.12.10

  Reaction of acetylide-silylene complex Cp*-(CO)(2)W(SiPh2)((CCBu)-Bu-t) (1a) with 4-(dimethylamino)-pyridine (DMAP) gave an equilibrium mixture of DMAP-stabilized silylene acetylide complexes trans- and cis-Cp*-(CO)(2)W(SiPh2 center dot DMAP)((CCBu)-Bu-t) (trans-4 and cis-4). The corresponding reaction using Cp*(CO)(2)W(SiPh2)(CCSiMe3) (2) produced the novel DMAP-coordinated silenylcarbyne/silylvinylidene complex Cp*(CO)(2)W[CC(SiPh2 center dot DMAP)(SiMe3)] (6a) as a major product, which was equilibrated with trans- and cis-Cp*(CO)(2)W(SiPh2 center dot DMAP)(CCSiMe3) (trans-5a and cis-5a) via silylene/silyl migration. The novel structures of cis-4 and 6a were revealed by X-ray crystallography. A mixture of 2 and pyridine exhibited interesting temperature-dependent NMR spectral changes, indicating the formation of trans- and cis-Cp*(CO)(2)W(SiPh2 center dot py)(CCSiMe3) (trans-5b and cis-5b) and Cp*(CO)(2)W[CC(SiPh2 center dot py)(SiMe3)] (6b) at low temperature, while a mixture of la and pyridine showed no such spectral changes.