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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Conjugate Addition/[3,3] Sigmatropic Shift Processes for Formation of Medium-Ring Cyclic Amines - Do They Circumvent
Phillip P Painter1, Matthew R Siebert1, Dean J Tantillo1
1Department of Chemistry, University of California-Davis , 1 Shields Avenue, Davis, California 95616 United States.
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.
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