Discovery of a Long-Range Perlin Effect in a Conformationally Constrained Oxocane
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† †Department of Chemistry and Biochemistry and §Department of Biological and Environmental Sciences, Samford University, Birmingham, Alabama 35229, United States
‡ Department of Chemistry & Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
∥ Department of Chemistry, University of Alabama at Birmingham, Birmingham, Alabama 35294, United States
*E-mail: [email protected]
Abstract
Herein, we present the crystal structure, NMR J analysis, and conformational and natural bond order analyses of tricyclic oxocane (1), resulting in the discovery of a long-range Perlin effect at C4 and C5. The normal Perlin effect (NPE) of Δ1JC–H = 18.38 Hz at C5 is the largest to date for a nonanomeric methylene due to an unprecedented through-space n → σ* stabilizing interaction. The NPE at C4 where Δ1JC–H = 6.91 Hz is nearly double those found in cyclohexanone.
Cited By
This article is cited by 3 publications.
- Robert Lee, Bryan Bashrum, Ethan C. Cagle, Jillian Walters, Jake Massey, Monica Zanghi, Carolyn Birchfield, David French, Jessica Joy, Gabriel dos Passos Gomes, Paul A. Wiget. Electronic Donation or Steric Contraction: A Spectroscopic and Structural Analysis of Medium-Sized Constrained Rings for Potential Long-Range Hyperconjugation. The Journal of Organic Chemistry 2019, 84 (16) , 9897-9906. https://doi.org/10.1021/acs.joc.9b00979
- Kahlil S. Salome, Cláudio F. Tormena. Revisiting the Long-Range Perlin Effect in a Conformationally Constrained Oxocane. The Journal of Organic Chemistry 2018, 83 (17) , 10501-10504. https://doi.org/10.1021/acs.joc.8b00935
- Clementina M.M. Santos, Artur M.S. Silva. Eight-Membered Rings With One Oxygen Atom. 2022, 44-84. https://doi.org/10.1016/B978-0-12-409547-2.14816-4