Discovery of a Long-Range Perlin Effect in a Conformationally Constrained Oxocane

摘要

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 C-4 and C-5. The normal Perlin effect (NPE) of Delta(1)J(C-H) = 18.38 Hz at C-5 is the largest to date for a nonanomeric methylene due to an unprecedented through space n -> sigma* stabilizing interaction. The NPE at C-4 where Delta(1)J(C-H) = 6.91 Hz is nearly double those found in cyclohexanone.