α-lithioacetonitrile | 20428-58-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: α-lithioacetonitrile
• 英文别名: lithium acetonitrilate；acetonitrile; lithium salt；N-lithioethyleneimine；lithium;ethenylideneazanide
• CAS: 20428-58-4
• 化学式: C₂H₂N*Li
• 分子量: 46.9856
• InChiKey: LTKCLJNDWMKKPC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.65
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  α-lithioacetonitrile 、 methyl (E)-2-(((dimethylamino)methylene)amino)-4,5-dimethoxybenzoate 在 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 生成 4-羟基-6,7-二甲氧基-3-喹啉甲腈
  参考文献：
  名称：

  Synthesis and Structure–Activity Relationships of 3-Cyano-4-(phenoxyanilino)quinolines as MEK (MAPKK) Inhibitors

  摘要：

  A series of 3-cyano-4-(phenoxyanilino)cyanoquinolines has been prepared as MEK (MAP kinase kinase) inhibitors. The best activity is seen with alkoxy groups at both the 6- and 7-positions. The lead compounds show low nanomolar IC50's against MAP kinase kinase, and have potent inhibitory activity in tumor cells. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0960-894x(00)00580-1

文献信息

• An Immucillin-Based Transition-State-Analogous Inhibitor of tRNA-Guanine Transglycosylase (TGT)
  作者：Christoph Hohn、Adrian Härtsch、Frederik Rainer Ehrmann、Toni Pfaffeneder、Nils Trapp、Oliver Dumele、Gerhard Klebe、François Diederich

  DOI：10.1002/chem.201600883

  日期：2016.5.10

  small‐molecule drug design. Herein, we report a transition‐state analogue, a small, immucillin‐derived inhibitor, as a new lead structure with a novel mode of action. The complex inhibitor synthesis was accomplished in 18 steps with an overall yield of 3 %. A co‐crystal structure of the inhibitor bound to Z. mobilis TGT confirmed the predicted conformation of the immucillin derivative in the enzyme active site

  志贺氏菌病是世界上最严重的腹泻病之一，到目前为止，没有任何有效的治疗方法。tRNA-鸟嘌呤转糖基酶（TGT）酶已被确定为小分子药物设计的有希望的目标。在本文中，我们报道了一种过渡态类似物，一种小的，由imuccillin衍生的抑制剂，是一种具有新颖作用方式的新型先导结构。复杂抑制剂的合成分18步完成，总收率为3％。与运动发酵单胞菌TGT结合的抑制剂的共晶结构证实了酶活性位点中imimcillin衍生物的预期构象。
• Additions of anionic nucleophiles to carbonyl compounds: Cation and e-lectrophile nature influence on ionic association vs carbonyl complexation control
  作者：A. Loupy、M.C. Roux-Schmitt、J. Seyden-Penne

  DOI：10.1016/s0040-4039(01)90411-3

  日期：1981.1

  the reaction of benzaldehyde mth LiCH2CN in THF is controlled by carbonyl complexation while uith KCH2CN the reaction is controlled by ionic association. In the reaction of m.Cl.C6H4CHCN−Li+ with substituted benzaldehydes carbonyl complexation prevails with p.CH3OC6H4CHO while ionic association dominates uith PhCHO and p.CNC6H4CHO.

  LiCH 2 CN在THF中的苯甲醛反应通过羰基络合控制，而KCH 2 CN则通过离子缔合控制反应。在m.Cl.C的反应6 ħ 4 CHCN -李+与取代的苯甲醛羰基络合盛行与p.CH 3 OC 6 H ^ 4 CHO而离子缔合占优势uith苯甲醛和p.CNC 6 ħ 4 CHO。
• A novel route to 3-alkylated estra-1,3,5(10)-trienes
  作者：Hermann Künzer、Manfred Thiel

  DOI：10.1016/s0040-4039(00)86669-1

  日期：1988.1

  Nucleophilic attack by the lithium anion of acetonitrile on the diastereomeric chromium tricarbonyl complexes of 17β-(tert-butyldimethylsilyloxy)-3-methoxyestra-1,3,5(10)-triene leads to the corresponding 3-cyanomethyl complexes, useful intermediates en route to 3-alkylated estra- 1,3,5(10)-trienes.

  乙腈锂阴离子对17β-（叔丁基二甲基甲硅烷基氧基）-3-甲氧基estra-1,3,5（10）-三烯的非对映体三羰基铬三羰基配合物的亲核攻击导致相应的3-氰基甲基配合物生成3-烷基化的雌二醇-1,3,5（10）-三烯。
• The Porphyrinogen−Porphodimethene Relationship Leading to Novel Synthetic Methodologies Focused on the Modification and Functionalization of the Porphyrinogen and Porphodimethene Skeletons
  作者：Lucia Bonomo、Euro Solari、Rosario Scopelliti、Carlo Floriani、Nazzareno Re

  DOI：10.1021/ja000253s

  日期：2000.6.1

  The general synthetic methods presented in this paper make available, on a preparative scale, unprecedented porphyrinogen-derived skeletons, including their functionalization at the meso positions. The stepwise dealkylation of meso-octaalkylporphyrinogen R8N4H4 [R = Et, 1; R = Bu-n, 2] was chemically, mechanistically, and structurally followed until the formation of porphomethene and porphodimethene derivatives 5-13, obtained with a sequential use of SnCl4. In particular, the porphodimethene derivative [(Et6N4)SnCl2], 9, was reductively transmetalated using Li metal to Et6N4Li2. 14, subsequently hydrolyzed to Et6N4H2, 15. The porphodimethene-nickel complex [(Et6N4)Ni], 16, was used for studying the reactivity and the ligand modification of the porphodimethene skeleton. The reactivity of 16 toward nucleophiles led to otherwise inaccessible meso-substituted-meso-functionalized porphyrinogens [(Et6N4R2)NiLi2], [R = H, 18; R = Bu-n, 19; R = CH2CN, 20], thus exemplifying a general methodology to meso-functionalized porphyrinogens. In addition, when [NMe2](-) was used as the nucleophile, 16 was converted into mono- and bis-vinylideneporphyrinogen derivatives [Et-4(=CHMe)N-4}NiLi] 21, and [Et-5(=CHMe)(2)N-4}NiLi2], 22, through the intermediacy of meso-(dimethylamino)-porphyrinogens undergoing an alpha-II elimination from the meso positions. Such intermediates were isolated and characterized in the stepwise reaction of 14 with LiNMe2 leading to [Et-6(NMe2)(2)N-4}Li-4], 23, and [Et-5(NMe2)(=CHMe)N-4}Li-4], 25. Both compounds, as a function of the reaction solvent, undergo the thermal elimination of HNMe2 with the formation of [Et-4(=CHMe)(2)N-4}Li-4], 24, which is then protonated to [Et-4(=CHMe)(2)N-4}H-4], 27. Transmetalation from 23 to 24 can be used as the methodology for the synthesis of a remarkable variety of meso-substituted and functionalized porphyrinogen complexes. The deprotonation of 16 is reversible, therefore 22 and 23 can be protonated back to their starting materials. We took advantage of the nucleophilicity of the vinylidene carbon in 21 and 22 fur establishing a general synthetic method to produce meso-functionalized porphodimethenes. This approach was exemplified with the alkylation and the benzoylation of 22 and 21 leading to [(E4Pr2N4)-N-i)Ni], 28, [Et-4CH(Me)(PhCO)}(2)N4Ni], 29, and [Et-5CH(Me)(PhCO)}N4Ni], 30, respectively. Complex 21 displays a bifunctional behavior, as shown by the formation of 30, whereas in the reaction with LiBu, led to [Et-5(Bu-n)(=CHMe)N-4}NiLi2], 31.
• Boutonnet, Jean-Charles; Rose-Munch, Francoise; Rose, Eric, Bulletin de la Societe Chimique de France, 1987, # 4, p. 640 - 648
  作者：Boutonnet, Jean-Charles、Rose-Munch, Francoise、Rose, Eric、Semra, Assia

  DOI：——

  日期：——