Structural features of aliphatic N-nitrosamines of 7-azabicyclo[2.2.1]heptanes that facilitate N-NO bond cleavage
Structural features of aliphatic N-nitrosamines of 7-azabicyclo[2.2.1]heptanes that facilitate N-NO bond cleavage
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DOI：
10.1021/ja010917d
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发表时间：
2001-10-24
影响因子：
15
通讯作者：
Inagaki, S
中科院分区：
文献类型：
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作者：
Ohwada, T;Miura, M;Inagaki, S
N-亚硝胺可以被认为是潜在的一氧化氮（NO）/亚硝鎓离子（NO+）供体。然而，N-亚硝胺，特别是脂肪族N-亚硝胺的结构与NO或NO+释放特性的关系仍不清楚。在这里，我们表明，脂肪族N-亚硝基胺的7-氮杂双环[2.2.1]庚烷可以进行异裂N-NO键断裂。基于对溶液中N-NO键转动势垒降低和固态中N-亚硝基的氮锥结构的观察，我们推测N-NO键的断裂是由于N-NO基团共振的降低而增强的。计算研究表明，7-氮杂双环[2.2.1]庚烷的N-亚硝胺的这些结构特征来自于施加在CNC角上的角应变。
N-Nitrosamines can be considered as potential nitric oxide (NO)/nitrosonium ion (NO+) donors. However, the relation of the structures of N-nitrosamines, in particular of aliphatic N-nitrosamines, to the characteristics of release of NO or NO+ remains unclear. Here we show that aliphatic N-nitrosoamines of 7-azabicyclo[2.2.1]heptanes can undergo heterolytic N-NO bond cleavage. On the basis of the observation of reduced rotational barriers of the N-NO bonds in solution and nitrogen-pyramidal structures of the N-nitroso group in the solid state, we postulate that N-NO bond cleavage of N-nitrosamines is enhanced by a reduction of the resonance in the N-NO group. Computational studies suggest that these structural features of the N-nitrosamines of 7-azabicyclo[2.2.1]heptane are derived from angle strain imposed on the CNC angles.