An experimental and quantumchemical study of [2+3] cycloaddition between (Z)-C-(m,m,p-trimethoxyphenyl)-N-(p-methyphenyl)-nitrone and (E)-3,3,3-trichloro-1-nitroprop-1-ene: mechanistic aspects

Abstract

C H R O N I C L E A B S T R A C TAnalysis of addent interactions with respect to the theory of electrophilicity and nucleophilicity indexes and kinetic studies shows the polar nature of,3-trichloro-1-nitroprop-1-ene. However, PES exploration results do not confirm any zwitterion on the reaction paths. On the other hand, the nature of the solvent effect and the experimentally determined activation parameter values do not exclude a scenario in which one-step and stepwise processes occur simultaneously.

On the question of zwitterionic intermediates in 1,3-dipolar cycloadditions between hexafluoroacetone and sterically crowded diazocompounds

“…Hybrid functional B3LYP with the 6-31G(d) basis set included in the GAUSSIAN 09 package [13] was used. Recently published reports show, that the same theoretical level was used successfully for the mechanistic study of series one-step [14][15][16][17][18][19] and two-step [5,6,20] 1,3-dipolar cycloadditions as well as different reactions involving fluororganic compounds [21][22][23]. In addition, similar simulations using more advanced B3LYP/6-31+G(d), B3LYP/6-31G(d,p) as well as B3LYP/6-311G(d) theoretical levels were performed.…”

A Full Regioselective and Stereoselective Synthesis of 4‐Nitroisoxazolidines via Stepwise [3 + 2] Cycloaddition Reactions between (Z)‐C‐(9‐Anthryl)‐N‐arylnitrones and (E)‐3,3,3‐Trichloro‐1‐nitroprop‐1‐ene: Comprehensive Experimental and Theoretical Study

“…In general, the reactions of aldonitrones with nitroethene or its 2‐substituted analogs lead to 4‐nitroisoxazolidines. During the cycloaddition reaction, a mixture of both theoretically possible diastereoisomeric [3 + 2] cycloadducts is formed (3,4‐ cis adduct as major product and 3,4‐ trans adduct as minor product).…”

“…In this way, among others, are proceeding [3 + 2] cycloadditions of ( E )‐3,3,3‐trichloro‐1‐nitroprop‐1‐ene ( 1 ) with ( Z )‐ C , N ‐diphenylnitrone , ( Z ) ‐C ‐(3,4,5‐trimethoxyphenyl)‐ N ‐methylnitrone and with ( Z )‐ C ‐(3,4,5‐trimethoxyphenyl)‐ N ‐(4‐methylphenyl)‐nitrone . We assumed, that a proportion of the 3,4‐ trans isomer in the postreaction mixture could be increased dramatically by replacing the previously tested nitrones by a compound with a relatively large volume substituent on the carbon atom of the CNO fragment.…”

“…However, it should be noted, that kinetic studies and density functional theory (DFT) calculations indicate that aforementioned reactions () proceed by a polar mechanism, with a highly asynchronous transition state. But in no instance, this is a stepwise mechanism, examples of which have been recently described in the previous literature .…”

DFT study of the decomposition reactions of nitroethyl benzoates catalyzed by the 1,3-dimethylimidazolium cation

“…Recently published reports 26,[44][45][46][47][48] , indicate that a similar approach was used successfully for the exploration of a reaction involving several different nitrocompounds. These calculations proved that the first step of the decomposition of nitroethyl benzoate (1a) is the establishment of a pre-reaction complex ( [1][DMIM]) between the ester molecule and the 1,3-dimethylimidazolium cation.…”