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

作者：Berry Ellen; Gomes Gabriel dos Passos; MacLean Alex; Martin Justin R; Wiget Paul A^*

来源：Journal of Organic Chemistry, 2016, 81(13): 5740-5744.

DOI：10.1021/acs.joc.6b00819

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.

• 出版日期2016-7-1