An abnormal spin-spin coupling of vinylic-allylic protons generated by a constraint of configuration

In a system where a rigid or frozen conformation constrains an allylic proton to orient nearly perpendicular to the plane of the olefinic bond, the allylic spin coupling may become comparable to, or greater than, the vicinal spin coupling. This anomalous situation is demonstrated in three series of compounds: the adducts of diazoalkanes to 1,2-diazepines, 4-piperidinocycloalk-2-en-1-one oximes and heterobicyclo[3,2,0]hept-3,6-dienes, where the NMR spectra have been well established by decoupling experiments.