Similarity and competition between multicomponent reactions with similar mechanisms and leading to similar scaffolds can be a useful tool for medicinal chemistry. In this review, we have summarized the studies disclosing the mechanism of such competition between the Biginelli and Hantzsch reactions. We focused our attention in particular on those studies exploiting similarity and competition as an opportunity to switch from one reaction to another, by simply changing the reaction conditions, thus opening the possibility to obtain, using the same experimental setup, molecular libraries of both 3,4-dihydropyrimidin-2-(1H)-ones (DHPM) and 1,4-dihydropyridines (1,4-DHP) scaffolds. The aim of this review is to encourage further exploitation of such synthetic strategy as a tool for enhancing the chemical space in medicinal chemistry.
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