(E)-N,N'-diisopropyloct-2-ynamidine

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (E)-N,N'-diisopropyloct-2-ynamidine
• 英文别名: (E)-N,N'-diisopropyloct-2-ynimidamide；N,N'-di(propan-2-yl)oct-2-ynimidamide
• 化学式: C₁₄H₂₆N₂
• 分子量: 222.374
• InChiKey: LJBSIPGKMZJZEL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  24.4
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1-庚炔 、 N,N'-二异丙基碳二亚胺 在 C₈₄H₁₁₀N₁₀Zn₂ 作用下， 以 氘代苯 为溶剂， 生成 (E)-N,N'-diisopropyloct-2-ynamidine
  参考文献：
  名称：

  碳二亚胺的锌催化氢元素化（HE；E = B、C、N 和 O）：中间体分离和机理见解

  摘要：

  共轭双胍（CBG）负载的氢化锌，[{LZnH} 2；L = {(ArHN)(ArN)-C=N–C=(NAr)(NHAr); Ar = 2,6-Et 2 -C 6 H 3 }] ( 1 ) (预)催化E-H (E = B、C、N和O)加成至碳二亚胺。化合物1用频那醇硼烷(HBpin)、末端炔烃、伯胺和醇催化碳二亚胺还原，得到一系列高转化率的N-硼基甲脒、丙啶脒、胍和异脲。所有这些反应都表现出良好的官能团耐受性。这些反应通过活性催化剂和脒酸锌中间体（Zn-1 , Zn-1′、和Zn-3）、炔基锌（Zn-2和Zn-2'）、苯胺锌（Zn-4）和醇锌（Zn-5）配合物，已通过多核 NMR 和 HRMS 分析进行了表征。此外，化合物Zn-1'、Zn-2'、Zn-4和Zn-5通过单晶 X 射线衍射研究得到证实。基于明确的中间体和化学计量实验，提出了完整的催化循环。

  DOI：

  10.1021/acs.organomet.2c00610

文献信息

• Catalytic Addition of Terminal Alkynes to Carbodiimides by Half-Sandwich Rare Earth Metal Complexes
  作者：Wen-Xiong Zhang、Masayoshi Nishiura、Zhaomin Hou

  DOI：10.1021/ja0560027

  日期：2005.12.1

  addition of terminal alkynes to carbodiimides has been achieved for the first time by use of half-sandwich rare earth metal complexes, such as Me2Si(C5Me4)(NPh)}Y(CH2SiMe3)(THF)2, which offers a straightforward, atom-economic route to the N,N'-disubstituted propiolamidines which contain a conjugated C-C triple bond, a new family of amidines which were difficult to prepare by other means. A rare earth metal

  通过使用半夹心稀土金属络合物，如 Me2Si(C5Me4)(NPh)}Y(CH2SiMe3)(THF)2，首次实现了末端炔烃与碳二亚胺的催化加成，这提供了一种直接的，原子经济路线到包含共轭 CC 三键的 N，N'-二取代丙脒，这是一种难以通过其他方式制备的新脒族。稀土金属脒物被证实是该过程中真正的催化物，从而首次证明脒单元虽然经常用作各种有机金属配合物的辅助配体，但本身可以参与催化反应。适当的条件。
• CNC-Pincer Rare-Earth Metal Amido Complexes with a Diarylamido Linked Biscarbene Ligand: Synthesis, Characterization, and Catalytic Activity
  作者：Xiaoxia Gu、Xiancui Zhu、Yun Wei、Shaowu Wang、Shuangliu Zhou、Guangchao Zhang、Xiaolong Mu

  DOI：10.1021/om500354s

  日期：2014.5.12

  In preparation of CNC-pincer rare-earth metal amido complexes with a diarylamido linked biscarbene ligand, it is found that conditions have a key influence on final products. Reaction of a THF suspension of bis[2-(3-benzylimidazolium)-4-methylphenyl]amine dichlorides (H3LCl2) with [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) (RE = Yb, Eu, Sm) in THF at room temperature afforded the only unexpected fused-heterocyclic compound 8,9-dibenzyl-3,14-dimethyl-8a,9-dihydro-8H-benzo[4,5]imidazo-[2',1':2,3]imidazo[1,2-a]imidazo[2,1-c]quinoxaline (1) containing an imidazolyl ring and a piperidyl ring, which formed through carbene C-C and C-N coupling. However, the reaction of H3LCl2 with [(Me3Si)(2)N](3)Er(mu-Cl)Li(THF)(3) in toluene afforded the CNC-pincer erbium amido complex incorporating a diarylamido linked biscarbene ligand LEr[N(SiMe3)(2)](2) (2) in low yield and the above fused-heterocyclic compound 1. The stepwise reaction of H3LCl2 with strong bases (n-BuLi or LiCH2SiMe3) in THF for 4 h, followed by treatment with [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3), generated zwitterion complexes [L2RE][REClN(SiMe3)(2)}(3)] (L = [4-CH3-2-(C6H4CH2-[N(CH)(2)CN]}C6H3](2)N; RE = Y (3), Er (4), Yb (5)) in less than 20% yields together with fused-heterocyclic compound 1. Additionally, the reaction of H3LCl2 with 6 equiv of NaN(SiMe3)(2) in THF for 4 h, followed by treatment with YbCl3, generated a novel discrete complex [L2Yb][Na(mu-N(SiMe3)(2))}(5)(mu(5)-Cl)] (6). The one-pot reaction of H3LCl2 with n-BuLi, followed by reaction with [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) in THF at -78 degrees C, generated the CNC-pincer lanthanide bisamido complexes LRE[N(SiMe3)(2)](2) (RE = Er (2), Y (7), Sm (8), Eu (9)) in moderate yields. These kinds of biscarbene supported pincer bisamido complexes could also be prepared by a one-pot reaction of bis(imidazolium) salt (H3LCl2) with 5 equiv of NaN(SiMe3)(2), followed by treatment with RECl3, in good yields at -78 degrees C. Investigation of the catalytic activity of complexes 2 and 7-9 indicated that all complexes showed a high activity toward the addition of terminal alkynes to carbodiimides producing propiolimidines, which represents the first example of rare-earth metal CNC-pincer-type catalysts applied for catalytic C-H bond addition of terminal alkynes to carbodiimides at room temperature.
• Zinc Catalyzed Hydroelementation (HE; E = B, C, N, and O) of Carbodiimides: Intermediates Isolation and Mechanistic Insights
  作者：Rajata Kumar Sahoo、Arukela Ganesh Patro、Nabin Sarkar、Sharanappa Nembenna

  DOI：10.1021/acs.organomet.2c00610

  日期：——

  The conjugated bis-guanidinate (CBG) supported zinc hydride, [LZnH}2; L = (ArHN)(ArN)-C═N–C═(NAr)(NHAr); Ar = 2,6-Et2-C6H3}] (1) (pre)-catalyzed addition of E–H (E = B, C, N, and O) to carbodiimides is presented. Compound 1 catalyzed the reduction of carbodiimides with pinacolborane (HBpin), terminal alkynes, primary amines, and alcohols, gave a series of N-boryl formamidines, propiolamidines, guanidines

  共轭双胍（CBG）负载的氢化锌，[LZnH} 2；L = (ArHN)(ArN)-C=N–C=(NAr)(NHAr); Ar = 2,6-Et 2 -C 6 H 3 }] ( 1 ) (预)催化E-H (E = B、C、N和O)加成至碳二亚胺。化合物1用频那醇硼烷(HBpin)、末端炔烃、伯胺和醇催化碳二亚胺还原，得到一系列高转化率的N-硼基甲脒、丙啶脒、胍和异脲。所有这些反应都表现出良好的官能团耐受性。这些反应通过活性催化剂和脒酸锌中间体（Zn-1 , Zn-1′、和Zn-3）、炔基锌（Zn-2和Zn-2'）、苯胺锌（Zn-4）和醇锌（Zn-5）配合物，已通过多核 NMR 和 HRMS 分析进行了表征。此外，化合物Zn-1'、Zn-2'、Zn-4和Zn-5通过单晶 X 射线衍射研究得到证实。基于明确的中间体和化学计量实验，提出了完整的催化循环。