The skeleton of the helianane's family is an unsolved controversial topic. Recent synthetic studies and 13 C NMR structural analysis have demanded for an amendment of helianane to the open ring curcudiol. However, some authors argue that the original helianane structure, a benzofused eight-membered ether ring system, cannot be ruled out immediately without further spectral analyses of curcudiol and helianane. The fact that this compound is extremely rare, obtained only from marine organisms, makes remote the possibility of reisolation. Therefore, we decided to approach this problem computationally. Herein, we performed a complementary quantum mechanical study in order to provide more information about the helianane's actual skeleton. Our 13 C NMR chemical shifts calculations suggests that the curcudiol structure is more likely to be the correct one. In addition, we simulated the formation pathways for both products starting from the known biosynthetic precursor. The results show that curcudiol is around 8.0 kcal mol −1 more stable than the originally proposed helianane structure. Comprehensive work suggesting the amendment of helianane to the open ring curcudiol by means of computational spectroscopy and thermodynamic reasons.