A molecular electron density theory investigation of the molecular mechanism, regioselectivity, stereoselectivity and chemoselectivity of cycloaddition reaction between acetonitrile N-oxide and 2,5-dimethyl-2H-[1,2,3]diazarsole

Mpro-SARS-CoV-2 Inhibitors and Various Chemical Reactivity of 1-Bromo- and 1-Chloro-4-vinylbenzene in [3 + 2] Cycloaddition Reactions

“…From the BET study the following appealing conclusions can be obtained: (i) the IRC associated with the 32CA reactions of BrVB 1 and ClVB 2 with BzNO 3 are divided into fourteen phases, which clearly indicates that the behavior of these one-step mechanism is non-concerted; (ii) the reaction begins with the depopulation of the N-C triple bond of BzNO 3. This feature is identical to that found in the 32CA reaction between acetonitrile N-oxide and 2,5-dimethyl-2H- [1][2][3] diazarsole [72]; (iii) formation of the C1 pseudoradical center takes place in Phase I (B-1) and (C-2), while the formation of the C3 pseudoradical center begins in the same Phase I (B-4) and (C-4); (iv) formation of the first C1-C3 single bond begins in B-7 and C-5, by sharing the non-bonding electron density of the two C1 and C3 pseudoradical carbons; (v) formation of the second O-C2 single bond begins at the end of the reaction paths in Phases IX and X, at a O-C2 distance of 2.14 Å for the 32CA reaction of BrVB 1, and 2.13 Å for the 32CA reaction of ClVB 2, via the donation of part of the non-bonding electron density of oxygen O of the NO framework to C2 carbon of these alkenes; (vi) these behaviors make it possible to conclude that these zw-type 32CA reactions follow a non-concerted two-stage one-step mechanism [73], as the formation of the second O-C single bond begins after the formation of about 90% of the first C1-C3 single bond.…”

Molecular docking, elucidating the regiospecificity and the mechanism of [3+2] cycloloaddition reaction between azidobenzene and propiolaldehyde

“…It is commonly used for modeling chemical reactions in addition to predicting chemical reactivity 8 . This concept has been applied in several surveys to explain how reactive cycloaddition mechanisms work [9][10][11][12][13][14][15][16][17][18][19][20] .…”

Exploration of the Mechanism, Chemospecificity, Regiospecificity and Stereoselectivity of the Cycloaddition Reaction between Hydroxyparthenolide and Nitrilimine: MEDT Study

“…Very recent studies of cycloaddition show the existence of a correlation between the electronic structure of dipoles and their reactivity.This makes it possible to classify 32CA reactions into four types: pdr type, pmr-type, zw-type and cb-type [30][31][32].…”