(E)-but-2-enedinitrile;2-(tert-butylsulfanylmethyl)pyridine;palladium | 279688-55-0

• 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: (E)-but-2-enedinitrile;2-(tert-butylsulfanylmethyl)pyridine;palladium
• CAS: 279688-55-0；279688-45-8；214759-13-4
• 化学式: C₁₄H₁₇N₃PdS
• 分子量: 365.795
• InChiKey: MYSPPXQDZURHTM-JITBQSAISA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  、 、 反丁烯二腈 在 哌啶 作用下， 以 氯仿 为溶剂， 生成 (E)-but-2-enedinitrile;2-(tert-butylsulfanylmethyl)pyridine;palladium
  参考文献：
  名称：

  Kinetics and mechanism of regioselective amination of the 1-phenylallyl group in cationic palladium(II) complexes bearing bidentate ligands

  摘要：

  The complexes [Pd(eta (3)-1-PhC3H4)(L-L')(=) [L-L' = 2-(PPh2)C6H4-1-CH=N (R = Me (1a), i-Pr (1b), t-Bu (1c), (R)-bornyl (1d), C6H4OMe-4 (1e), C6H3Me2-2,6 (1f), C6H3(i-Pr)(2)-2,6 (1g)), 6-MeC5H3N-2-CH=NC6H4OMe-4 (2a), C5H4N-2-CH=N-t-Bu (2b) and C5H4N-2-CH2S-t-Bu (3a)] are generally present in solution as two geometrical isomers, the relative abundance of which depends essentially on the steric requirements of the L-L' ligand. In the presence of fumaronitrile the cationic complexes undergo a regioselective amination by secondary amines HY at the CH, allyl terminus, yielding [Pd(eta (2)-fn)(L-L')] and the allylamines (E)-PhCH=CHCH2Y. Under pseudo-first-order conditions the amination rates (k(obs)) are found to depend on the k(2)[HY] term for 2a and 3a, and on the sum k(2)[HY] + k(3)[HY](2) for the other complexes. The second-order term k(2) is related to direct nucleophilic attack on the CH, allyl terminus of the substrate whereas the third-order term k(3) is ascribed to parallel attack by a further HY molecule on the intermediate [Pd(1-PhC3H4)(L-L')(HY)](+). The k(2) values depend on the steric and electronic properties of both the amine HY and the ligand L-L'. For complexes 1a-1g, the relatively higher k(2) values and their increase with increasing steric crowding at the nitrogen-bonded carbon of substituent R are interpreted in terms of a greater reactivity of the isomer with the CH2 allyl terminus trans to phosphorus and cis to the NR group. The high amination rate of 2a, as compared with that of 2b, is related to substantial steric interaction of the CH2 allyl terminus with the 6-Me pyridine group in close proximity in the predominant isomer. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(01)00333-4