2,2-dimethylpent-3-enylamine | 87156-68-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2,2-dimethylpent-3-enylamine
• 英文别名: 2,2-Dimethylpent-3-en-1-amine；2,2-dimethylpent-3-en-1-amine
• CAS: 87156-68-1
• 化学式: C₇H₁₅N
• mdl: MFCD19207143
• 分子量: 113.203
• InChiKey: BZUCXFUCSDECFX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.52
• 重原子数：
  8.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.714
• 拓扑面积：
  26.02
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2,2-dimethylpent-3-enylamine 、 对甲苯磺酰氯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 N-(2,2-dimethyl-pent-3-enyl)-p-toluenesulfonamide
  参考文献：
  名称：

  供体配体在第3组金属催化的氨基化反应中的作用

  摘要：

  检查了一系列供体配体对第3族金属催化的分子内烯烃加氢胺化的作用。证明环化令人惊讶地耐受几个配位官能团的存在，表明在第3族金属催化过程的反应条件方面有更大的自由度。

  DOI：

  10.1016/j.tetlet.2012.09.019
• 作为产物：
  描述：

  2,2-dimethyl-1-amino-pent-4-ene 在 bis(trimethylsilyl)amide yttrium(III) 、 sodium t-butanolate 作用下， 以21%的产率得到2,2-dimethylpent-3-enylamine
  参考文献：
  名称：

  供体配体在第3组金属催化的氨基化反应中的作用

  摘要：

  检查了一系列供体配体对第3族金属催化的分子内烯烃加氢胺化的作用。证明环化令人惊讶地耐受几个配位官能团的存在，表明在第3族金属催化过程的反应条件方面有更大的自由度。

  DOI：

  10.1016/j.tetlet.2012.09.019

文献信息

• Palladium-catalyzed oxidation of amino alkenes to cyclic imines or enamines and amino ketones
  作者：B. Pugin、L. M. Venanzi

  DOI：10.1021/ja00361a023

  日期：1983.11

  n NH 2 (n=3,4) se cyclisent en pyrrolines-1 ou tetrahydro-3,4,5,6 pyridines dans les conditions du procede Wacker. Les aminoalcenes avec un groupe amino secondaire donnent les imines cycliques correspondantes, tandis que les alcenes avec un groupe amino tertiaire donnent des aminocetones

  Lesaminoalcenes du type CH 2 =CH(CH 2 ) n NH 2 (n=3,4) se cyclisent en pyrrolines-1 ou tetrahydro-3,4,5,6 pyridines dans les conditions du procede Wacker。Lesaminoalcenes avec un groupe amino secondaire donnent les imines cycliquesrespondantes, tandis que les alcenes avec un groupeamino tertiaire donnent desaminocetones
• Enabling Bifunctionality and Hemilability of N-Heteroaryl NHC Complexes
  作者：Zephen G. Specht、Sara A. Cortes-Llamas、Hai N. Tran、Christoffel J. van Niekerk、Khing T. Rancudo、James A. Golen、Curtis E. Moore、Arnold L. Rheingold、Tammy J. Dwyer、Douglas B. Grotjahn

  DOI：10.1002/chem.201100521

  日期：2011.6.6

  Functionalized carbene ligands: Increasing the steric bulk of R1 on 1 from H to tBu results in lengthening of the MN bond (by up to 9 %), lowered activation energy for chelate opening (cf. 2) by 17 kcal mol−1, and improved binding of an amine and intramolecular hydrogen bonding (3). Iridium species with R1=tBu are effective catalysts of base‐free intramolecular hydroamination, unlike less‐hindered

  官能碳烯配体：增加空间体积的R 1上1从H到Ť卜导致延长M的（高达9％）N键，用于螯合开口（参见降低活化能2由17千卡摩尔）-1，并改善了胺与分子内氢键的结合（3）。R 1 = t Bu的铱物种是无碱分子内加氢胺化的有效催化剂，与受阻较弱的类似物不同。
• Efficient Intramolecular Hydroamination of Unactivated Alkenes Catalysed by Butyllithium
  作者：Ali Ates、Coralie Quinet

  DOI：10.1002/ejoc.200300058

  日期：2003.5

  In this communication, we wish to report some preliminary results demonstrating, for the first time, that intramolecular hydroamination of unactivated alkenes can be performed efficiently using small quantities of nBuLi as the pre-catalyst. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003

  在这篇通讯中，我们希望报告一些初步结果，首次证明使用少量 nBuLi 作为预催化剂可以有效地进行未活化烯烃的分子内加氢胺化。((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003
• Effects of Hindrance in N-Pyridyl Imidazolylidenes Coordinated to Iridium on Structure and Catalysis
  作者：Zephen G. Specht、Douglas B. Grotjahn、Curtis E. Moore、Arnold L. Rheingold

  DOI：10.1021/om400758b

  日期：2013.11.11

  The unhindered N-pyrid-2-yl imidazolidene NHC ligand has been shown to chelate to a Cp*Ir fragment (1). With the goal of weakening the coordination of the pyridyl substituent and enabling its role as pendant base or hemilabile ligand, a tert-butyl group at C-6 next to the pyridyl N was installed. Attempted coordination of the newly synthesized carbene ligand avoided N-coordination entirely, but led to unexpected C-metalation at C-3 by the Cp*Ir center. Successful formation of a weakly N-coordinated analogue was achieved by synthesizing a ligand with a second tert-butyl group at C-4. The complexes were studied using X-ray crystallography and NMR spectroscopy. The X-ray crystal structure of di-tert-butyl analogue 6 showed that in the solid the complex existed as a chloride-bridged dimer, with the pyridyl nitrogen uncoordinated. In solution, N-15 chemical shift information revealed that 6 existed with the pyridyl substituent N-coordinated, presumably as a monomer, but that addition of an amine ligand readily opened the chelate. Finally, 6 was used as a catalyst for intramolecular hydroamination of primary and secondary alkenylamines. Comparing (heteroaryl)NHC species, each with a tert-butyl group next to the nitrogen, which enables hydroamination, the rate differences are very modest but increase in the order imidazolyl < pyridyl < pyrimidyl, which may be an effect of basicity but because of the similarity in rates is better ascribed to counterbalancing of more than one factor, including hemilability. The (4,6-di-tert-butyl)pyridyl species 6 was shown to be much more effective compared to parent compound 1 without the tert-butyl groups, in which the chelating group was more tightly bound.