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On the Origin of Cis Selectivity in the Cyclization of N-Protected 2-Substituted 3-Aza-5-hexenyl Radicals: A Density Functional Study
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Section:Abstract
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.
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- Published In Issue March 05, 2004
- Received September 23, 2003
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