Understanding the different reactivity of (Z)- and (E)-β-nitrostyrenes in [3+2] cycloaddition reactions. An MEDT study

Abstract

The different reactivity and selectivities of isomeric E/Z β-nitrostyrenes in polar zw-type [3+2] cycloaddition reactions is explained within MEDT.

Unveiling the [3+2] cycloaddition between difluoromethyl diazomethane and 3-ylideneoxindole from the perspective of molecular electron density theory

“…A similar result for the B3LYP functional was recently obtained in the study of the endo / exo stereoselectivity of ( Z )- and ( E )-β-nitrostyrenes participating in 32CA reactions. 71 Moreover, CCSD predicts also too low endo stereoselectivity , showing that even higher-order electron correlation treatments are needed for reaching an improved quantitative agreement.…”

Understanding the Participation of Fluorinated Azomethine Ylides in Carbenoid-Type [3 + 2] Cycloaddition Reactions with Ynal Systems: A Molecular Electron Density Theory Study

“…Analysis of the E / Z configuration of DFAYs 14 and 18 indicates that the ( E ) configuration is the most stable (see Section 1 in the Supporting Information). This is a fundamental question because the reactivity of Z / E -isomeric bent TACs presents a different reactivity in cycloaddition processes. , The ELF localization domains, basin attractor positions, and Lewis-like structures of ( E ) DFAYs 14 and 18 are shown in Figure .…”

“…This is a fundamental question because the reactivity of Z/Eisomeric bent TACs presents a different reactivity in cycloaddition processes. 24,25 The ELF localization domains, basin attractor positions, and Lewis-like structures of (E) DFAYs 14 and 18 are shown in Figure 1.…”

Elucidating the Mechanism and Selectivity of [3+2] Cycloaddition: A DFT and Molecular Docking Investigation of the Reaction of 6-Butoxy-5,6- Dihydro-4H-1,2-Oxazine 2-Oxide with Dimethyl Maleate

“…In 2016, Domingo introduced the molecular electron density theory (MEDT) [8], which offers insights into how changes in electron density influence molecular reactivity. Over the past seven years, the MEDT framework has been employed to analyze various facets of 32CA reactions, encompassing regio- [9], stereo- [9][10][11][12], and chemoselectivity [13,14], reactivity [15][16][17], substituent effects [18,19], and other critical aspects [20][21][22]. In this study, a comprehensive MEDT investigation of the 32CA reaction between nitrone 1 and dimethyl maleate 2 (Scheme 1) is presented.…”