© 2020 Elsevier Ltd The total synthesis of selaginellin S, isolated from Selaginella pulvinata, was achieved via a concise route including Diels-Alder reaction and dehydrogenative aromatization. The NMR analysis of the synthetic compound confirmed the structure of natural selaginellin S. Although the natural compound was reported to have an axial chirality, the absence of the axial chirality of selaginellin S at ambient temperature was suggested from lineshape changes in variable temperature NMR experiments with the pivaloyl derivative of the synthetic compound.