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FMO Approach in [4 + 2] Cycloadditions. Kinetic Studies with 1,2‐Dimethylenecyclopentane
Author(s) -
Sustmann Reiner,
SiangouriFeulner Ioana
Publication year - 1993
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19931260525
Subject(s) - chemistry , diene , stereospecificity , homo/lumo , kinetic energy , computational chemistry , stereochemistry , organic chemistry , molecule , catalysis , physics , quantum mechanics , natural rubber
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 k 2 values and 1/( E Homo – E LUMO ). The cycloadditions of E/Z isomeric dienophiles to 1 are stereospecific. These reactions are best described in terms of concerted processes.