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Mechanism studies of the chemoselective ring opening of N-tosyl aziridines with aldehydes catalyzed by an N-heterocyclic carbene under aerobic conditions

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Abstract

The mechanism of the reaction of N-tosyl aziridines with aldehyde catalyzed by nucleophilic carbene under aerobic conditions was investigated using B97D method. Two pathways were studied based on experimental reports, and the results show the first pathway is the best one. In the first pathway, the aziridine ring-opening step is the rate-determining step with the free energy of 18.3 kcal mol−1. The addition step of one oxygen molecule to olefin forms the singlet state compound. The oxygen molecule in this system can be utilized as a source of an oxygen atom for the carboxylate product.

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Acknowledgments

The work described in this paper was supported by the Foundation of Henan Educational Committee of China (No. 16A150044) and the Foundation of Xuchang University of China (No. 2015102).

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Xuchang University of China, No.88 of Bayi Road, Xuchang, 461000, Henan, People’s Republic of China

    Chunhui Liu & Peilin Han

  2. School of Medicine and Pharmacy, Ocean University of China, No.5 of Yushan Road, Qingdao, 266003, Shandong, People’s Republic of China

    Yankai Liu

  3. The College of Chemistry and Molecular Engineering, Center of Computational Chemistry, Zhengzhou University of China, No.100 of Science Road, Zhengzhou, 450001, Henan, People’s Republic of China

    Mingsheng Tang

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  1. Chunhui Liu
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  2. Peilin Han
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Correspondence to Chunhui Liu.

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Liu, C., Han, P., Liu, Y. et al. Mechanism studies of the chemoselective ring opening of N-tosyl aziridines with aldehydes catalyzed by an N-heterocyclic carbene under aerobic conditions. Theor Chem Acc 135, 59 (2016). https://doi.org/10.1007/s00214-016-1820-1

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