Question

FMO approach of cycloaddition 4+2 system​

Answer 1

Answer:

Abstract

Kinetic measurements on [4 + 2] cycloadditions of 1,2‐dimethylenecyclopentane (1) as a model diene for normal Diels‐Alder reactions are described. This diene was selected in order to check whether a synperiplanar diene is a good test case for the FMO model. Using HOMO and LUMO energies from semi‐empirical quantumchemical calculations, we indeed obtained a good linear correlation between the lg k2 values and 1/(EHomo – ELUMO). The cycloadditions of E/Z isomeric dienophiles to 1 are stereospecific. These reactions are best described in terms of concerted processes.

Answer 2

Kinetic measurements on [4 + 2] cycloadditions of 1,2‐dimethylenecyclopentane (1) as a model diene for normal Diels‐Alder reactions are described. This diene was selected in order to check whether a synperiplanar diene is a good test case for the FMO model. Using HOMO and LUMO energies from semi‐empirical quantumchemical calculations, we indeed obtained a good linear correlation between the lg k2 values and 1/(EHomo – ELUMO). The cycloadditions of E/Z isomeric dienophiles to 1 are stereospecific. These reactions are best described in terms of concerted processes.