THE DIMERIZATION OF 2-METHOXYCARBONYLBUTA-1,3-DIENE - THE IMPORTANCE OF PARALOCALISATION ENERGY IN ASSESSING DIENE REACTIVITY

Authors
SPINO C CRAWFORD J CUI YP GUGELCHUK M
Citation
C. Spino et al., THE DIMERIZATION OF 2-METHOXYCARBONYLBUTA-1,3-DIENE - THE IMPORTANCE OF PARALOCALISATION ENERGY IN ASSESSING DIENE REACTIVITY, Perkin transactions. 2, (6), 1998, pp. 1499-1506
Citations number
35
Categorie Soggetti
Chemistry Physical","Chemistry Inorganic & Nuclear
Journal title
Perkin transactions. 2 → ACNP
ISSN journal
03009580
Issue
6
Year of publication
1998
Pages
1499 - 1506
Database
ISI
SICI code
0300-9580(1998):6<1499:TDO2-T>2.0.ZU;2-W
Abstract
The dimerisation and competitive cycloaddition of 2-methoxycarbonylbut a-1,3-diene with electron-rich dienes has been investigated. Experimen tal results provide evidence that the enthalpy of the pi-system signif icantly influences the energy of the transition state of cycloaddition s of this type. This has been corroborated by ab initio calculations. We propose an early reorganisation of the pi-electrons in such cycload ditions to explain the influence stated above.