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On the Question of the Regio-Orientation, Stereo-Orientation and Molecular Mechanism in the Cascade

Mikołaj Sadowski¹, Ewa Dresler², Radomir Jasiński³

¹Cracow University of Technology, CUT Doctoral School, Faculty of Chemical Engineering and Technology, Warszawska 24, 31-155 Cracow, Poland.

International Journal of Molecular Sciences

|September 27, 2025

Abstract:

Sulfur-containing heterocyclic structures play an important role in modern biotechnology. Their synthesis is made possible by means of the hetero Diels-Alder reaction involving unsaturated sulfur compounds. In the framework of this paper, the molecular mechanism of the cycloaddition reactions between tioanalogs of the butadiene generated in situ with the participation of the Lawesson reagent and the E-2-phenyl-1-nitroethene was evaluated on the basis of the DFT quantum chemical calculations. It was found that the most favored reaction path is realized according to a stepwise mechanism with the participation of the zwitterionic intermediate. To study this further, the molecular mechanism of the deamination process of the primary cycloadducts was also analyzed. It was found that this mechanism is substantially different to the case of other known β-elimination processes and is achieved via a stepwise scheme. In addition to these investigations, the LA catalysis of the deamination process was also explored.

Keywords:

Lewis acid (LA) catalysis cycloaddition deamination density functional theory hetero Diels–Alder reaction nitroalkene stepwise mechanism

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