Electronic Donation or Steric Contraction: A Spectroscopic and Structural Analysis of Medium-Sized Constrained Rings for Potential Long-Range Hyperconjugation

Electronic Donation or Steric Contraction: A Spectroscopic and Structural Analysis of Medium-Sized Constrained Rings for Potential Long-Range Hyperconjugation

Herein, we report the 1 J CH analyses, natural bond orbital analyses, and X-ray crystal structures of a number of C, O, and N constrained tricyclic cycles. These experiments provide access into the nature of the apparent Perlin effect previously reported in constrained tricyclic cycles, as well as e...

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Bibliographic Details
Published in:Journal of organic chemistry Vol. 84; no. 16; pp. 9897 - 9906
Main Authors: Lee, Robert, Bashrum, Bryan, Cagle, Ethan C, Walters, Jillian, Massey, Jake, Zanghi, Monica, Birchfield, Carolyn, French, David, Joy, Jessica, dos Passos Gomes, Gabriel, Wiget, Paul A
Format: Journal Article
Language:English
Published: United States American Chemical Society 16-08-2019
Online Access:Get full text
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Summary:Herein, we report the 1 J CH analyses, natural bond orbital analyses, and X-ray crystal structures of a number of C, O, and N constrained tricyclic cycles. These experiments provide access into the nature of the apparent Perlin effect previously reported in constrained tricyclic cycles, as well as evidence suggesting both steric contraction and long-range hyperconjugation account for the observed 1 J CH perturbations. We report a true Perlin effect of 10.9 Hz in an azocane and large steric effect resulting in Δ1 J C–H = 10.9 Hz in a cyclooctane.
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ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.9b00979