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Merging and bifurcation of 4+2 and 2+4 cycloaddition modes in the archetypal dimerization of butadiene. A case of competing bispericyclic, pericyclic and diradical paths

Authors :
Silvano Romano
Pierluigi Caramella
Lucio Toma
Paolo Quadrelli
Source :
Tetrahedron Letters. 43:8785-8789
Publication Year :
2002
Publisher :
Elsevier BV, 2002.

Abstract

The dimerization of butadiene has been explored by using DFT methods at the B3LYP level with the 6-311+G** basis set. A concerted bispericyclic TS for the endo pathway and a concerted pericyclic TS for the exo pathway are the lowest passes for the dimerization and occur at almost the same energy thus accounting for the lack of stereochemical preferences in the dimerization. Diradical paths involving two unswitched transoid butadiene moieties are competing and account for the formation of minor amounts of trans-1,2-divinyl cyclobutane and 1,5-cycloctadiene.

Details

ISSN :
00404039
Volume :
43
Database :
OpenAIRE
Journal :
Tetrahedron Letters
Accession number :
edsair.doi...........922857970862924604dad0aab4949620