2-allyl-2-(p-tolyl)pent-4-enenitrile | 59242-97-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-allyl-2-(p-tolyl)pent-4-enenitrile
• 英文别名: 2-(4-Methylphenyl)-2-prop-2-enylpent-4-enenitrile
• CAS: 59242-97-6
• 化学式: C₁₅H₁₇N
• 分子量: 211.307
• InChiKey: SMYFFXPOZKIBGT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-allyl-2-(p-tolyl)pent-4-enenitrile 在 Grubbs catalyst first generation 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以92%的产率得到1-p-tolylcyclopent-3-ene-1-carbonitrile
  参考文献：
  名称：

  (±)-α-Cuparenone 的高效实用全合成

  摘要：

  描述了作为 (±)-α-cuparenone 全合成关键步骤的一锅环戊环化方法。

  DOI：

  10.1055/s-2007-990899
• 作为产物：
  描述：

  allyl allyl((4-methylphenyl)ethynyl)carbamate 在 N,O-双三甲硅基乙酰胺 、 二乙基甲氧基硼烷 、 palladium diacetate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 甲苯 为溶剂， 以80%的产率得到2-allyl-2-(p-tolyl)pent-4-enenitrile
  参考文献：
  名称：

  通过自动串联催化Pd催化的N -Alloc- N-烯丙基酰胺的重排：可逆C–N活化和Pd（0）加速的Ketenimine Aza-Claisen重排的证据

  摘要：

  的自动串联催化双烯重排ň -alloc- ň烯丙基ynamides开发。该反应通过两个分开且不同的催化循环进行，同时发生脱羧性Pd-π-烯丙基和Pd（0）促进的aza-Claisen重排。由计算支持的详细机理研究突出了这两个独立的机制。以前未报告的可逆C–N电离和Pd（0）催化的[3,3]-σ重排被发现。这项研究为π-烯丙基和σ重排提供了新的反应途径。

  DOI：

  10.1021/acs.orglett.0c04078

文献信息

• β-SiH-Containing Tris(silazido) Rare-Earth Complexes as Homogeneous and Grafted Single-Site Catalyst Precursors for Hydroamination
  作者：Naresh Eedugurala、Zhuoran Wang、KaKing Yan、Kasuni C. Boteju、Umesh Chaudhary、Takeshi Kobayashi、Arkady Ellern、Igor I. Slowing、Marek Pruski、Aaron D. Sadow

  DOI：10.1021/acs.organomet.6b00956

  日期：2017.3.27

  A series of homoleptic rare-earth silazido compounds and their silica-grafted derivatives were prepared to compare spectroscopic and catalytic features under homogeneous and interfacial conditions. Trivalent tris(silazido) compounds LnN(SiHMe2)tBu}(3) (Ln = Sc (1), Y (2), Lu (3)) are prepared in high yield by salt metathesis reactions. Solution-phase and solid-state characterization of 1-3 by NMR and IR spectroscopy and X-ray diffraction reveals Ln-H-Si interactions. These features are retained in solvent coordinated 2 center dot Et2O, 2 center dot THF, and 3 center dot THF. The change in spectroscopic features characterizing the secondary interactions (v(s1H), (1)J(siH)) from the unactivated SiH in the silazane HN(SiHMe2)tBu follows the trend 3 > 2 > 1 approximate to 2 center dot THF approximate to 3 center dot THF. Ligand lability follows the same pattern, with Et2O readily dissociating from 2 center dot Et2O while THF is displaced only during surface grafting reactions. I and 2 center dot THF graft onto mesoporous silica nanoparticles (MSN) to give LnN(SiHMe2)tBu}(n)@MSN (Ln = Sc (1@MSN), Y (2@MSN)) along with THF and protonated silazido as HN(SiHMe2)tBu and H(2)NtBu. The surface species are characterized by multinuclear and multidimensional solid-state (SS) NMR spectroscopic techniques, as well as diffuse reflectance FTIR, elemental analysis, and reaction stoichiometry. A key (1)J(SiH) SSNMR measurement reveals that the grafted sites most closely resemble Ln.THF adducts, suggesting that siloxane coordination occurs in grafted compounds. These species catalyze the hydroamination/bicyclization of aminodialkenes, and both solution-phase and interfacial conditions provide the bicyclized product with equivalent cis:trans ratios. Similar diastereoselectivities mediated by catalytic sites under the two conditions suggest similar effective environments.