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2004 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 69, no 5, p. 1487-1491Article in journal (Refereed) Published
Abstract [en]
Cyclization of the N-dimethylphosphinoyl-2-methyl-3-aza-5-hexenyl radical has been studied at the UB3LYP/6-31+G(d)//UB3LYP/6-31G(d) hybrid density functional level. The corresponding radical precursor has been synthesized and found to give cis/trans ratios of up to 10/1 in reductive radical cyclizations. The relative energies of reactant and transition state conformers were determined. In discord with the Beckwith-Houk model, it has been found that chair-axial transition states, which lead to cis products, are lowest in energy, rationalizing the observed experimental diastereoselectivity.
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-90422 (URN)10.1021/jo030294h (DOI)14987001 (PubMedID)
2003-05-122003-05-122017-12-14Bibliographically approved