Unravelling the mechanism of the organocatalyzed aminolytic kinetic resolution of α-nitroepoxides: a theoretical study,Catalysis Science & Technology

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Unravelling the mechanism of the organocatalyzed aminolytic kinetic resolution of α-nitroepoxides: a theoretical study
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2020/01/16 , DOI: 10.1039/c9cy01800j
Amedeo Capobianco _{1,

2,

3,

4} , Sara Meninno _{1,

2,

3,

4} , Alessandra Lattanzi _{1,

2,

3,

4}

Affiliation

The aminolytic kinetic resolution of 2-methyl-2-nitro-3-phenyl oxirane with aniline was investigated by quantum chemical computations. It has been assessed that the reaction proceeds via a concerted ring opening/elimination of nitrous acid mechanism. The results are in agreement with the experimental findings when using the Takemoto's catalyst, which is estimated to perform in a highly efficient manner in the kinetic resolution of this class of epoxides in the absence of any background reaction. H-Bonding, π–π and CH/π interactions appear to make a significant contribution to the formation of a ternary complex and a transition state, which preferentially facilitates the reaction of the (2R,3S)-nitroepoxide to the α-amino ketone, leaving (2S,3R)-nitroepoxide unreacted.

中文翻译：

阐明α-硝基环氧化物有机催化氨基分解动力学拆分的机理：理论研究

通过量子化学计算研究了2-甲基-2-硝基-3-苯基环氧乙烷与苯胺的氨基分解动力学拆分。已经估计该反应通过协调的开环/亚硝酸消除机制进行。该结果与使用Takemoto催化剂时的实验结果相符，据估计，在没有任何背景反应的情况下，该催化剂可以高效地实现此类环氧化物的动力学拆分。H键，π–π和CH /π相互作用似乎对三元络合物和过渡态的形成做出了重要贡献，这优先促进了（2 R，3 S）-硝基环氧化物与α-氨基酮，残留（2 S，3 R）-硝基环氧化物未反应。

更新日期：2020-03-09

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