Owing to the negligible or acceptable immunogenicity, small molecules capable of inducing the differentiation of undifferentiated stem cells into organ-specific cell types are particularly promising in developing replacement therapy, but such compounds with undescribed architectures are extremely rare. Selesconol (1) is discovered from the culture of Daldinia eschscholzii IFB-TL01 as a skeletally unprecedented inducer for the differentiation of rat bone marrow mesenchymal stem cells into neural cells, with its unique framework clarified to derive from the intermediate tautomerization of the dalesconol A biosynthetic pathway.