title: Conjugate Addition/[3,3] Sigmatropic Shift Processes for Formation of Medium-Ring Cyclic Amines - Do They Circumvent the Woodward-Hoffmann Rules?
abstract: Herein we describe our exploration, using density functional theory calculations, of a conjugate addition-rearrangement sequence that leads to medium-ring cyclic amines. On the basis of the results of our calculations, we conclude that the rearrangement step is rate determining. In addition, we analyze the role of a carbanion lone pair in the rearrangement step, concluding that it functions as a substituent on a [3,3] sigmatropic shift, rather than a nucleophile; thus, the Woodward-Hoffmann rules are not circumvented in this reaction via involvement of orthogonal orbitals on an atom involved in the rearrangement.
authors.affiliation: Department of Chemistry, University of California-Davis , 1 Shields Avenue, Davis, California 95616 United States.
authors.forename: Phillip P
authors.initials: PP
authors.lastname: Painter
authors.affiliation: Department of Chemistry, University of California-Davis , 1 Shields Avenue, Davis, California 95616 United States.
authors.forename: Matthew R
authors.initials: MR
authors.lastname: Siebert
authors.affiliation: Department of Chemistry, University of California-Davis , 1 Shields Avenue, Davis, California 95616 United States.
authors.forename: Dean J
authors.initials: DJ
authors.lastname: Tantillo