Kinetic aspects of [3+2] cycloaddition reactions between (E)-3,3,3-trichloro-1-nitroprop-1-ene and ketonitrones

Abstract

Kinetic measurements show that despite their polar nature, cycloaddition reactions of (E)-3,3,3-trichloro-1-nitroprop-1-ene with ketonitrones take place according to a mechanism that proceeds without intervention of zwitterionic intermediate. This is indicated by the values of activation parameters (activation enthalpy, activation entropy) and the nature of the kinetic solvent effect.

Recent progress in the field of cycloaddition reactions involving conjugated nitroalkenes

“…Reaction between properly 2-subsitued of nitroethene and (Z)-C- ( 25 (Table 8). Kinetic studies indicate that all these cycloadditions do take place according to a mechanism that proceeds without intervention of zwitterionic intermediate 26 . In recent time, gem-1,1-dinitroethene became the object of research as a highly reactive and useful π-deficient three atoms components.…”

Regioselectivity, stereoselectivity, and molecular mechanism of [3 + 2] cycloaddition reactions between 2-methyl-1-nitroprop-1-ene and (Z)-C-aryl-N-phenylnitrones: a DFT computational study

“…All calculations were carried out at the same level of theory that was used to study the 32CA reactions of different type of nitrones and 2-substituted nitroethenes. It is important to note that good correlations between the calculated parameters of the critical structures [27,32,42], the results of a comprehensive kinetic study (Eyring parameters) [34,42], the nature of solvent effects [34,42], and a quantitative description of secondary isotope effects [43] were obtained when this level of theory was applied. This suggests that the B3LYP/6-31G(d) level can accurately illustrate the nature of the critical structures in the cycloaddition process of interest in the present work.…”

“…These reactions have been also explored in detail using various theoretical approaches [21,22,26]. Additionally, similar cycloadditions of 1-substituted nitroethenes (such as 2nitroprop-1-ene [27], 1-chloronitroethene [28,29], and 1bromonitroethene [27]) and 2-substituted nitroethenes (e.g., (E)-2-arylnitroethenes [30,31], (E)-1-nitroprop-1-ene [32], (E)-3,3,3-trichloro-1-nitroprop-1-ene [27,33,34], (E)-3,3,3trifluor-1-nitroprop-1-ene [35], and (E)-3-nitroacrylate [27]) analogs have been explored. Recently, preliminary studies of 32CA processes between 1,2-disubstituted nitroethenes and (Z)-(3,4,5-trimethoxyphenyl)-N-methylnitrone have also been published [28,36].…”

Novel functionalized β-nitrostyrenes: Promising candidates for new antibacterial drugs

“…The presence of a strongly electron-withdrawing (EWG) nitro group at a vinyl moiety stimulates substantially the π-deficient character of their double bond. In consequence, CNA have a significant affinity to nucleophilic reagents as diazocompounds (Jasiński, 2015), nitrones (Jasiński and Mróz, 2015, Jasiński, 2015a), ylides (Jasiński, 2015b), 1,3-dienes (Łapczuk-Krygier et al, 2014, Jasiński, 2017), vinyl ethers (Jasiński et al, 2014) and many others. Additionally, the nitro group may be easily converted to many other functional groups (Ono, 2003).…”