Re-examining the mechanisms of competing pericyclic reactions of 1,3,7-octatriene. Academic Article

abstract

• DFT (both B3LYP and M06-2X), CASSCF, and CASPT2 calculations were used to investigate competing [3, 3] and [3, 5] sigmatropic shifts and intramolecular [4+2] cycloaddition of 1,3,7-octatriene. In accord with previous results on 1,5-hexadiene, CASSCF calculations found both stepwise and concerted pathways for the [3, 3] rearrangement. For the competing [3, 5] sigmatropic rearrangement, CASSCF and CASPT2 calculations revealed three stepwise pathways with similar barriers. UB3LYP and UM06-2X calculations predicted a different potential energy landscape: no stepwise [3, 3] pathway, only two competing [3, 5] sigmatropic shifts, and an intramolecular Diels-Alder cycloaddition/homolytic ring-opening pathway. Significant lowering of barriers for all rearrangements was predicted for some 1,3,7-octatrienes with substituents at the 4- and 7-positions.

authors

• Gutierrez Santacruz, Osvaldo

published proceedings

• Chemistry

author list (cited authors)

• Gutierrez, O., Harrison, J. G., Pemberton, R. P., & Tantillo, D. J.

citation count

• 6

complete list of authors

• Gutierrez, Osvaldo||Harrison, Jason G||Pemberton, Ryan P||Tantillo, Dean J

publication date

• January 2012

publisher

• Wiley  Publisher

published in

• Chemistry - A European Journal  Journal

keywords

• Density Functional Calculations
• Octatriene
• Radicals
• Sigmatropic Rearrangement
• Substituent Effects

PubMed Central ID

• 22836223

Digital Object Identifier (DOI)

• 10.1002/chem.201201193

start page

• 11029

end page

• 11035

volume

• 18

issue

• 35

URL

• http://dx.doi.org/10.1002/chem.201201193