lithium 2-(2-pyridyl)-2-propanolate | 155806-00-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: lithium 2-(2-pyridyl)-2-propanolate
• 英文别名: Li(2-(2'-pyridyl)propan-2-olate)；Lithium;2-pyridin-2-ylpropan-2-olate
• CAS: 155806-00-1
• 化学式: C₈H₁₀NO*Li
• 分子量: 143.114
• InChiKey: UPJBDRUJRSJGHM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.32
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  36
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  lithium 2-(2-pyridyl)-2-propanolate 、 三氯一氧化钒 三氯代氧化钒(V) 以 甲苯 、 正戊烷 为溶剂， 以58%的产率得到
  参考文献：
  名称：

  钒（IV）和-（V）与O，N-螯合的氨基酚盐和吡啶基醇盐的配体配合。

  摘要：

  应用了两种不同的单阴离子O，N螯合配体系统，即[OC6H2（CH2NMe2）-2-Me2-4,6]-（1）和[OCMe2（[2] -Py）]-（2）。在钒（V）配合物的合成中。1中的叔胺官能团通过[VOCl3]，[V（= NR）Cl3]或[V（= NR）（NEt2）3]导致钒核还原为4+氧化态（R = Ph， （3a，5a），R ＝对-Tol（3b，5b）），并且使用1作为还原剂导致钒（IV）配合物的合成[VO（OC6H2（CH2NMe2）-2-Me2-4， 6）2]（4）和[V（= NPh）（OC6H2（CH2NMe2）-2-Me2-4,6）2]（6）。在[V（= Np-Tol）（NEt2）（OC6H2（CH2NMe2）-2-Me2-4,6）2]（7b）的情况下，还原速度足够慢，无法通过1H NMR进行表征，并且温度研究表明，它是溶液中的五坐标物种。尽管1与[V（= Np-Tol）（Oi

  DOI：

  10.1021/ic991415s

文献信息

• Rhenium, Palladium, and Copper Pyridylalkoxide Complexes:  Synthesis, Structural Characterization, and Catalytic Application in Epoxidation Reactions
  作者：Gerhard M. Lobmaier、Guido D. Frey、Rian D. Dewhurst、Eberhardt Herdtweck、Wolfgang A. Herrmann

  DOI：10.1021/om700738f

  日期：2007.12.1

  starting from Pd(OAc)2 and [CuCl2·2(H2O)] complexes of the form [M(L)2] (M = Cu, Pd) (6a−g and 8a) were prepared. For complexes 6a and 8a molecular structures have been determined by single-crystal X-ray diffraction studies, which showed the expected square planar geometry with the pyridine ring nitrogens situated mutually in trans position. Complexes 3, 4, 6, and 8 were tested in the epoxidation reaction

  双（烷基/芳基）-2-吡啶基醇酸酯配体（a - g）与[ReOCl 4 ]（NBu 4）的反应导致形成通式为[ReOCl 3（L）]（NBu 4）的金属-氧配合物）（2，3）和[ReOCl（L）2 ]（4，5），其中L =双（烷基/芳基）-2- pyridylalcoholate。配合物2a，4a和5a的分子结构已经通过单晶X射线衍射研究确定。除了预期的4a晶体结构，其中一个配体的醇盐位点反式配位至Rhenyloxo片段，配合物5a显示了一个罕见的反式chloro-oxo [ReOCl（L）2 ]连接性的例子。另外，从Pd（OAc）2和[CuCl 2 ·2（H 2 O）]形式为[M（L）2 ]（M = Cu，Pd）（6a - g和8a）的配合物制备。对于配合物6a和8a，已经通过单晶X射线衍射研究确定了分子结构，该研究显示了预期的正方形平面几何结构，吡啶环氮原子相互位于反式位置。配合物3，
• Tungsten(VI) phenylimido alkylidene complexes containing a monoanionic O,N-chelating ligand and their isolated precursor complexes: x-ray structures of W(CH2SiMe3)3(:NPh)[OCPh2(2-py)] and W(:CHSiMe3)(CH2SiMe3)(:NPh)[OCPh2(2-py)]
  作者：Paul A. van der Schaaf、Robertus A. T. M. Abbenhuis、Walter P. A. van der Noort、Robin de Graaf、David M. Grove、Wilberth J. J. Smeets、Anthony L. Spek、Gerard van Koten

  DOI：10.1021/om00016a051

  日期：1994.4

  The lithium salts of selected phenoxides, with one or two potentially chelating o-CH2NMe2 substituents, 8-quinolinolate (8-quin), ortho-chelating arenethiolate ligands, and a-substituted 2-pyridylmethoxides, were reacted with W(CH2SiMe3)3Cl(=NPh) (1) and W(CH2SiMe3)2Cl-(=NPh)(OCMe3) (2), respectively. It appears that steric properties of the monoanionic O,N- and S,N-chelating ligands are very important for inducing an intramolecular H(alpha)-abstraction reaction; i.e., the phenoxide OC6H4CH2NMe2-2 (a) gave rise to the formation of alkylidene precursor W(CH2SiMe3)3(=NPh)(OC6H4CH2NMe2-2) (3), in which the alkyl groups are still intact, whereas the ''pincer phenolate'' OC6H2(CH2NMe2)2-2,6-Me-4 (b), with two o-CH2NMe2 substituents, directly led to the formation of alkylidene complex W(=CHSiMe3)(CH2SiMe3)(=NPh)(OC6H2(CH2NMe2)2-2,6-Me-4) (4'). The reaction of 1 with Na-8-quin instantaneously gave W(=CHSiMe3)(CH2SiMe3)(=NPh)(8-quin) (5'). Also, electronic properties play an important role in the formation of alkylidene complexes; i.e., the complexes derived from 2, containing a pi-electron-donating tert-butoxide group, are thermally more stable toward intramolecular H(alpha) abstraction than those derived from 1. With the alpha-substituted 2-pyridylmethoxide ligands OR1R2(2-py), in which the R substituents can be varied easily, we were able to prepare both the alkylidene precursor and the subsequent product of an intramolecular H(alpha)-abstraction reaction, the tungsten(VI) alkylidene complex. The solid-state structure (X-ray) of the trialkyltungsten(VI) precursor W(CH2SiMe3)3(=NPh)[OCPh2(2-py)] (9) as well as the resulting alkylidene complex W(=CHSiMe3)(CH2SiMe3)(=NPh)[OCPh2(2-py)] (9') have been determined. Crystals of 9 are monoclinic, space group P2(1)/c, with unit-cell dimensions a = 10.974(1) angstrom, b = 18.531(3) angstrom, and c = 20.307(2) angstrom, beta = 106.47(1)degrees, Z = 4, final R = 0.063, and R(w) = 0.053 for 2644 reflections with I > 2.5sigma(I) and 415 parameters. Crystals of 9' are triclinic, space group P1BAR, with unit-cell dimensions a = 9.4359(5) angstrom, b = 10-8887(7) angstrom, and c 16.611(1) alpha = 81.60(1)degrees, beta = 88.37(1)degrees, gamma = 79.19(1)degrees, Z=2, final R=0.042, and R(w) = 0.026 for 5879 reflections with I > 2.5sigma(I) and 348 parameters. The two molecular structures clearly show the advantage of a d0 metal center in forming an alkylidene unit out of two alkyl groups. The chemical shift of H-6, the hydrogen atom bonded at the ortho position with respect to the pyridyl nitrogen, as a probe shows that the pyridyl group in alkylidene complexes 9' and W(=CHSiMe3)(CH2SiMe3)(=NPh)[OCH(CMe3)(2-py)] (10') can coordinate intramolecularly in the syn rotamer, whereas in the anti rotamer this will lead to considerable steric hindrance of the SiMe3 group of the alkylidene function with the vicinal substituents in the chelating ring. The reactivity of the present tungsten(VI) alkylidene complexes 5', 9.', and 10' toward linear olefins is very low. However, aldehydes react with these complexes in Wittig-type reactions to yield predominantly the corresponding trans-olefin. Norbornene can be polymerized using these alkylidene complexes as a catalyst in a ring-opening metathesis reaction at 70-degrees-C to give polymeric cyclopentenes with greater-than-or-equal-to 90% cis vinylene bonds.