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.
Department(s)
Chemistry and Biochemistry
Document Type
Article
DOI
https://doi.org/10.1021/acs.joc.5b00996
Keywords
substituents, chemical structure, energy, rearrangement, conjugate acid-base pairs
Publication Date
2015
Recommended Citation
Painter, Phillip P., Matthew R. Siebert, and Dean J. Tantillo. "Conjugate Addition/[3, 3] Sigmatropic Shift Processes for Formation of Medium-Ring Cyclic Amines–Do They Circumvent the Woodward–Hoffmann Rules?." The Journal of organic chemistry 80, no. 23 (2015): 11699-11705.
Journal Title
The Journal of organic chemistry
