Work

Causation in a Cascade: The Origins of Selectivities in Intramolecular Nitrone Cycloadditions

Year: 2012

Type: article

Abstract: The factors controlling chemo-, regio-, and stereoselectivity in a cascade of reactions starting from a bis(cyanoalkenyl)oxime and proceeding via nitrone cycloadditions have been unraveled through a series of density functional theory calculations with several different functionals. Both kinetic and thermodynamic control of the reaction cascade are important, depending upon the conditions. Kinetic control was analyzed by the distortion/interaction model and found to be dictated by differences in distortions of the cycloaddends in the transition states. A new mechanism competing with that originally proposed in the application of these reactions to the histrionicotoxin synthesis was discovered in these studies.

Source: Journal of the American Chemical Society

DOI: 10.1021/ja300002k

Authors: Elizabeth H. Krenske, Sesil Agopcan, Viktorya Aviyente, K. N. Houk, Brian A. Johnson, Andrew B. Holmes