The Octant Rule. 7. Deuterium as an Octant Pertuber

Article abstract of DOI:10.1021/ja00526a038

(1S)-exo-2-Deuteriobicyclo<2.2.1>heptan-7-one (1) and (1S)-endo-2-deuteriobicyclo<2.2.1>heptan-7-one (2) were synthesized, and their circular dichroism spectra were measured and analyzed.Both ketones show dissignate Cotton effects near 295 nm corresponding to their n-?^* electronic transitions: 1 (Δε₂₉₆ = +0.033) and 2 (Δε₂₉₂ = +0.132).The nature of the isotopic perturbation on the n-?^* transitions of 1 and 2, related β-deuterioadamantanones and cyclohexanones, and α-deuteriocyclohexanones is treated theoretically.The net contribution to the sign of the rotatory strength is determined by the relatively more consignate contribution on the C-H bond that is located in an oppositely signed octant relative to the C-D bond.