The carbon and proton NMR chemical shifts and trajectories obtained using the DFT calculations reveal site dependent chemical environmental variation of the stereoisomers. In carbon-NMR, the most significant changes are the position of δ(C5), although chemical environments of all carbons (and protons) shift in the isomers. The δ(C5) is larger than the degenerated δ(C6, C7) in exo-JP-10-chair, but this position is reversed is exo-JP-10-boat, δ(C5) < δ(C6, C7). The through space interaction of the protons on the flag carbon (C5) and on the boat tip carbon (C10) of the exo-boat and boat-like configurations after the TS (i.e., the ∆C8C10C9 plane tilts up), highlights the importance of spatial arrangement in the determination of chemical environments. The detailed NMR analysis supports the conclusion that the exo-chair isomer is the more stable configuration due to its more symmetric and less strained arrangement of hydrogens and carbons.