Premium
Transitions of Electron Demand in Pericyclic Reactions: Normal, Neutral, and Inverse Diels–Alder Reactions of Polyhalogenated Cyclopentadienes
Author(s) -
Eibler Ernst,
Höcht Peter,
Prantl Bernhard,
Roßmaier Henry,
Schuhbauer Hans Markus,
Wiest Hubert,
Sauer Jürgen
Publication year - 1997
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.199719971209
Subject(s) - pericyclic reaction , chemistry , inverse , reactivity (psychology) , homo/lumo , diels–alder reaction , reaction rate constant , computational chemistry , catalysis , organic chemistry , molecule , kinetics , physics , medicine , alternative medicine , mathematics , geometry , pathology , quantum mechanics
Normal, neutral, and inverse‐type Diels‐Alder reactions can be observed in [4+2] cycloadditions of polyhalogenated cyclopentadienes 1a–1i with various aryl‐substituted cyclic and open‐chain dienophiles, and characteristic gradations of reactivity associated with the different mechanistic types are often displayed. Reaction rate constants and semiempirically derived HOMO and LUMO values for the reactants suggest that neutral [4+2] cycloadditions should be regarded as a transition between normal and inverse Diels‐Alder reactions.