Discovery of a Long-Range Perlin Effect in a Conformationally Constrained Oxocane.
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 Δ(1)JC-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 Δ(1)JC-H = 6.91 Hz is nearly double those found in cyclohexanone.
Ellen
E
Berry
Department of Chemistry & Biochemistry, Florida State University , Tallahassee, Florida 32306, United States.
Gabriel Dos Passos
Gdos P
Gomes
Alex
A
MacLean
Department of Chemistry, University of Alabama at Birmingham , Birmingham, Alabama 35294, United States.
Justin R
JR
Martin
Paul A
PA
Wiget