[Cu(tert-butoxycarbonyl-glycine-N,N-bis(picolyl)amide)Cl2] | 745784-32-1

• 英文名称: [Cu(tert-butoxycarbonyl-glycine-N,N-bis(picolyl)amide)Cl2]
• 英文别名: [Cu(Boc-Gly-bis[(2-pyridyl)methyl]amine)Cl2]；[Cu(Boc-Gly-bpa)Cl2]
• CAS: 745784-32-1
• 化学式: C₁₉H₂₄Cl₂CuN₄O₃
• 分子量: 490.877
• InChiKey: VLLWZNBKFIBDFP-UHFFFAOYSA-L

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

• 作为反应物：
  描述：

  甲醇 、 [Cu(tert-butoxycarbonyl-glycine-N,N-bis(picolyl)amide)Cl2] 以 甲醇 、 二氯甲烷 为溶剂， 生成 dichloro(N,N-di(2-pyridylmethyl)amine)copper(II)
  参考文献：
  名称：

  氮配位叔羧酰胺的化学性质：双（吡啶甲基）酰胺铜（II）配合物的光谱研究。

  摘要：

  叔羧酰胺的电中性氮原子的金属配位减少了CN键旋转的障碍，并使酰胺朝着甲醇分解的方向活化。X射线晶体学研究表明，该反应性与酰胺共振结构的提升和同时在氮处的锥体化有关。但是，尚未获得溶液中的机械数据。显而易见的是，结构迁移率是配合物的特征，并且晶体学数据并未完全说明相关的反应物种。在此报告中，我们总结了酰胺氮配位的双（吡啶甲基）酰胺与三氟甲磺酸铜（II）和氯化铜（II）的红外光谱，紫外可见光谱和EPR光谱。在非质子溶剂二氯甲烷和乙腈中采样的光谱之间的比较，以及在甲醇分解条件下揭示了溶液中形成的几种物质的性质。关键反应是（I）涉及CH3CN或CH3OH的配体交换，或者在IR实验中来自KBr的溴离子，（II）涉及氨基酸取代的配体Boc-Xaa-bpa（Boc ＝叔丁氧羰基，Xaa ＝分别为甘氨酸，丙氨酸和亮氨酸，bpa ＝双（吡啶甲基胺），（III）氯配体从LCuCl 2络合物中解离并形成方形-金字塔形络合物阳离子[LCuCl]

  DOI：

  10.1039/b516875a
• 作为产物：
  描述：

  (Boc)glycyldipicolylamide 、 copper(II) choride dihydrate 以 乙腈 为溶剂， 以85%的产率得到[Cu(tert-butoxycarbonyl-glycine-N,N-bis(picolyl)amide)Cl2]
  参考文献：
  名称：

  The Activation of Tertiary Carboxamides in Metal Complexes: An Experimental and Theoretical Study on the Methanolysis of Acylated Bispicolylamine Copper(II) Complexes

  摘要：

  It is a well-established concept that the C-N bond cleavage of carboxamide functions is facilitated by the coordination of a metal ion to the carbonyl oxygen atom. In contrast, the alternative C-N bond activation by coordination of a neutral tertiary carboxamide nitrogen atom has not been studied. We present the first results on the effect of nitrogen pyramidalization in N-coordinated metal complexes on the methanolysis of tertiary carboxamide groups. An analysis of the reactions products obtained from the methanol cleavage of [(N-Acyl-bpa)Cu](2+) (bpa = N,N-bispicolylamine) complexes is presented together with experimental and high-level theoretically calculated structures. The strong effect of different anions on the amide pyramidalization and subsequent C-N-bond cleavage is evaluated. We show that dichloro complexes [(N-Acyl-bpa)CuCl2] have much less activated amide groups than the corresponding triflate species. They should therefore be less reactive. However, [(N-Acyl-bpa)CuCl2] complexes dissociate in solution to give cationic monochloro complexes [(N-Acyl-bpa)Cu(S)Cl](+) (S = solvent molecule). Theoretical calculations show that the amide pyramidalization in the monochloro complexes is equal to that in the corresponding CF3SO3- salts. Consequently, chloro and triflato complexes are cleaved with similar rates and efficiencies. Parallels to and differences in the reactivity of purely organic distorted amides are discussed.

  DOI：

  10.1021/ic0496774