**6. Conclusion**

The chemical space related to natural products is associated to important scientific findings in what to extent the discovery of important new chemical entities. In this sense, the genus *Caesalpinia* is a prolific source of secondary metabolites which also biosynthesize homoisofla‐ vonoids. In addition, only a few species are reported to produce dimers of homoisoflavonoids as secondary metabolites. Homoisoflavonoids and its dimers are classified as unusual natural products with strict occurrence in nature present the most diverse types of biological activities. These compounds are isolated through HPLC methods and identified by different techniques as NMR, UV, MS based on the biosynthesis of chalcones with an additional carbon provided by *S*‐methyl from methionine. It is important to highlight that these phenolic compounds are part of ethnopharmacological applications by people whose access and use the biodiversity for the improvement of health conditions are made for centuries. Furthermore, the investiga‐ tion of this class of phenolic compounds provides chemosystematics data for classification and discovery of pharmacologically efficient compounds from species of *Caesalpinia* spp.
