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A DFT study on the Sc(OTf)3 catalyzed hetero Diels–Alder reaction of N-tosylhydrazones and ortho-quinone methides: energetic aspects, selectivities, and molecular mechanism

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Abstract

In the present work, a DFT study was carried out on a Sc(OTf)3 catalyzed hetero Diels–Alder (HDA) reaction between an ortho-quinone methide (OQM) and N-tosylhydrazone (NTH), reported experimentally by Tang and co-workers, to shed light on the reactivities, selectivities, and molecular mechanism of the reaction. The results of CDFT and Parr functions analyses showed that Sc(OTf)3 enhances both global and local reactivities and increases the regioselectivity of the HDA reaction. This Lewis acid not only decreases the activation barriers but also changes the reaction mechanism from one-step to the stepwise with the formation of a zwitterionic intermediate. In addition, the first step of this reaction is rate-determining step, and in excellent agreement with the experimental results, the formation of the trans-cycloadduct is more favorable both kinetically and thermodynamically. NBO and IGMH analyses were described satisfactorily the trans-stereoselectivity predominance. The molecular mechanism of this polar stepwise reaction was studied by using ELF analysis, and it was found that both C4-N5 and C1-O6 single bonds are formed between the two fragments via the polarization of the lone electron pairs located over the heteroatom toward the carbon atom.

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Funding

This research was partially supported by the grant from Ayatollah Boroujerdi University with No. IR01-04–1403002369.

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  1. Chemistry Department, Faculty of Science, Ayatollah Boroujerdi University, Boroujerd, Iran

    Mousa Soleymani & Mahdieh Goudarzi

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  1. Mousa Soleymani
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All authors conceived and designed the calculations; analyzed and interpreted the data based on the considered softwares (Gaussian and Multiwfn); and wrote the paper.

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Correspondence to Mousa Soleymani.

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Soleymani, M., Goudarzi, M. A DFT study on the Sc(OTf)3 catalyzed hetero Diels–Alder reaction of N-tosylhydrazones and ortho-quinone methides: energetic aspects, selectivities, and molecular mechanism. Struct Chem 35, 497–509 (2024). https://doi.org/10.1007/s11224-023-02201-4

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