Neutral Monodentate and Hypervalent Chalcogen Bond Catalysis on the Intramolecular Rauhut‐Currier Reaction of Bis(enones): A DFT Study

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Recently, chalcogen bond catalysts with telluronium cations have garnered considerable attention in organic reactions. In this work, chalcogen bond catalysis on the bromination reaction of anisole with N‐bromosuccinimide (NBS) with the telluronium cationic catalysts has been explored with density functional theory (DFT). The catalytic reaction is divided into two stages: the bromine transfer step and the proton transfer step. Based on the computational results, one can find the rate‐determining step is the bromine transfer step. Moreover, the present study elucidates that a stronger chalcogen bond (ChB) between catalysts and NBS will give better catalytic performance. Additionally, this work also clarified the importance of the electrostatic and polarization effects in the chalcogen bond between the oxygen atom of NBS and the Te atom of the catalyst in this bromination reaction. The electrostatic and polarization effects are significantly influenced by the electron‐withdrawing ability of the substitution groups on the catalysts. Moreover, the structure‐property relationship between the strength of ChB bond, electrostatic effect, polarization effect and catalytic performance are established for the designation of more efficient chalcogen bond catalysts.

Chalcogen Bond Catalysis with Telluronium Cations for Bromination Reaction: Importance of Electrostatic and Polarization Effects

Wang,

Zhao,

Chen

et al. 2023

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Cationic Hypervalent Chalcogen Bond Catalysis on the Povarov Reaction: Reactivity and Stereoselectivity

Zhao,

Li,

Wang

et al. 2024

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Chalcogen bond catalysis, particularly cationic hypervalent chalcogen bond catalysis, is considered to be an effective strategy for organocatalysis. In this work, the cationic hypervalent chalcogen bond catalysis for the Povarov reaction between N‐benzylideneaniline and ethyl vinyl ether was investigated by density functional theory (DFT). The catalytic reaction involves the cycloaddition process and the proton transfer process, and the rate‐determining step is the cycloaddition process. Cationic hypervalent tellurium derivatives bearing CF3 and F groups exhibit superior catalytic activity. For the rate‐determining step, the Gibbs free energy barrier decreases as the positive electrostatic potential of the chalcogen bond catalysts increases. More importantly, the Gibbs free energy barrier has a strong linear correlation with the electrostatic energy of the chalcogen bond in the catalyst‐substrate complex. Furthermore, the catalytic reactions include the endo pathway and exo pathway. The C‐H···π interaction between the substituent of the ethyl vinyl ether and the aryl ring of the N‐benzylideneaniline contributes to the endo‐selectivity of the reaction. This research contributes to a deeper understanding of chalcogen bond catalysis, providing insights for designing chalcogen bond catalysts with high performance.

Hypervalent Chalcogen Bonds Catalysis on the Intramolecular Aza‐Michael Reaction of Aminochalcone: Catalytic Performance and Chalcogen Bond Properties

Wang,

Shi,

Zhao

et al. 2024

Chalcogen bond (ChB) catalysis, as a new type in the field of non‐covalent bond catalysis, has become a hot research topic in the field of organocatalysis in recent years. In the present work, we investigated the catalytic performance of a series of hypervalent ChB catalysis based on the intramolecular Aza‐Michael reaction of aminochalcone. The reaction includes the carbon‐nitrogen bond coupling step (key step) and the proton transfer step. The catalytic performance of mono‐dentate pentafluorophenyl chalcogen bond donor ChB1 was comparable to that of bis‐dentate chalcogen bond donor ChB4, and stronger than that of mono‐dentate chalcogen bond donors ChB2 and ChB3. The formation of the chalcogen bond between the catalyst and the carbonyl oxygen atom of the reactant, causing the charge rearrangement of the reactant and C(1) charge of the ‐C‐Ph group to become more positive, thereby the ChB catalysis promoted the nucleophile reaction. The electron density of the chalcogen bond of the pre‐complex, the most positive electrostatic potentials of the catalyst, and the NPA charge of the key atom are proportional to the Gibbs energy barrier of the C‐N bond coupling process, which provides an idea to predict the catalytic activity of the ChB catalysis.