3-Pyridylacetonitrile-2-d2 | 144467-09-4

• 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: 3-Pyridylacetonitrile-2-d2
• 英文别名: 2,2-Dideuterio-2-pyridin-3-ylacetonitrile
• CAS: 144467-09-4
• 化学式: C₇H₆N₂
• 分子量: 120.122
• InChiKey: OIPHWUPMXHQWLR-SMZGMGDZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  36.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-吡啶乙腈 在 cis-[Mn(2,6-bis(di-tert-butylphosphinomethyl)pyridine)(CO)₂] 、 重水 作用下， 以 甲苯 为溶剂， 反应 24.0h， 生成 3-Pyridylacetonitrile-2-d2
  参考文献：
  名称：

  锰-钳-催化腈水合、α-氘化和通过金属配体合作形成α-氘化酰胺

  摘要：

  报道了一种简单有效的系统，用于腈的水合和 α-氘化以形成酰胺、α-氘化腈和 α-氘化酰胺，该系统由能够进行金属-配体合作的地球丰富锰的单钳络合物催化。该反应具有选择性并且可以耐受多种官能团，从而以中等至良好的产率得到相应的酰胺。将溶剂从叔丁醇改为甲苯并使用 D 2 O 导致以高选择性形成 α-氘代腈。此外，可以一步直接从腈和 D 2 中获得 α-氘化酰胺O 在四氢呋喃中。初步的机理研究表明，这些转变通过金属-配体协同途径促进了腈的活化，生成锰酮亚胺和烯酰胺钳络合物作为进一步转变的关键中间体。

  DOI：

  10.1021/acscatal.1c01748

文献信息

• Structural study and reactivity of carbanions in solution: phenyl- and 3-pyridylacetonitriles
  作者：Denis Croisat、Jacqueline Seyden-Penne、Tekla Strzalko、Lya Wartski、Jacques Corset、Francoise Froment

  DOI：10.1021/jo00050a015

  日期：1992.11

  From the IR and C-13 NMR spectra of Li- or K-associated anionic species 1A,M formed from phenylacetonitrile in THF, it appears that monomeric tight ion pairs and THF-solvated aggregates are in equilibrium at 0.25 M concentration; the 0.025 M THF solution of IA,Li only contains the monomer, the Li cation being likely located near the N atom of the CN moiety. In toluene-THF or hexane-THF solvent mixtures, solvated aggregates are predominant In toluene-hexane, only desolvated aggregates are seen. Addition of increasing amounts of HMPA to THF solutions shows the formation of various Li solvates among which, according to low-temperature P-31 and Li-7 NMR determinations, the Li-di HMPA externally solvated ion pairs predominate. Solvent- or cryptand-separated ion pairs can also be characterized in DMSO or THF m the presence of cryptand. Li- or K-associated 3-pyridylacetonitrile anionic species 2A,M behave as IA,M in toluene, in DMSO, and in THF in the presence of HMPA or of cryptand. In THF, as for IA,Li, 2A,Li monomeric tight ion pairs are in equilibrium with THF-solvated aggregates at c = 0.25 M concentration, the Li cation interacting both with the CN moiety and the pyridyl ring; however, at c = 0.025 M aggregates are still present. IA,M and 2A,M (M = Li, K) aggregates or IA,Li and 2A,Li externally HMPA solvated ion pairs lead to predominant or exclusive 1,4-addition with benzylideneacetone. In THF 1,2-addition takes place with IA,Li while 2A,Li leads to exclusive 1,4 addition; this discrepancy could be due to the fact that the equilibrium between monomeric tight ion pairs and aggregates is different in the two cases and to the different structure of the tight ion pairs, especially the strength of the anion-cation interaction.
• Manganese-Pincer-Catalyzed Nitrile Hydration, α-Deuteration, and α-Deuterated Amide Formation via Metal Ligand Cooperation
  作者：Quan-Quan Zhou、You-Quan Zou、Sayan Kar、Yael Diskin-Posner、Yehoshoa Ben-David、David Milstein

  DOI：10.1021/acscatal.1c01748

  日期：2021.8.20

  A simple and efficient system for the hydration and α-deuteration of nitriles to form amides, α-deuterated nitriles, and α-deuterated amides catalyzed by a single pincer complex of the earth-abundant manganese capable of metal–ligand cooperation is reported. The reaction is selective and tolerates a wide range of functional groups, giving the corresponding amides in moderate to good yields. Changing

  报道了一种简单有效的系统，用于腈的水合和 α-氘化以形成酰胺、α-氘化腈和 α-氘化酰胺，该系统由能够进行金属-配体合作的地球丰富锰的单钳络合物催化。该反应具有选择性并且可以耐受多种官能团，从而以中等至良好的产率得到相应的酰胺。将溶剂从叔丁醇改为甲苯并使用 D 2 O 导致以高选择性形成 α-氘代腈。此外，可以一步直接从腈和 D 2 中获得 α-氘化酰胺O 在四氢呋喃中。初步的机理研究表明，这些转变通过金属-配体协同途径促进了腈的活化，生成锰酮亚胺和烯酰胺钳络合物作为进一步转变的关键中间体。