Diversity Oriented Synthesis and asymmetric aminocatalysis constitute two important tools to access new compounds of interest. The extraordinary development of these two areas has allowed chemists to populate new regions of chemical space. Therefore, new libraries of complex and diverse structures are available for the development of new drugs. In recent years, the term Aminocatalytic privileged-structure Diversity Oriented Synthesis (ApDOS) has been conceptualized, highlighting its potential towards the asymmetric synthesis and diversification of privileged structures, small base molecules of complex natural architectures that usually present important biological activities.

Herein, we present the development of new organocatalytic cascade reactions for the synthesis and diversification of privileged structures, using trienamine activation as a key step. An important feature of this process is that once it has been completed, it is possible to generate new reactive species within the same molecule. In this sense, a series of consecutive reactions can be carried out incorporating dienophiles with an addition-nucleophilic functionality. As a result, complex and diverse compounds can be accessed through simple starting materials. It should be noted that, under this methodology, it will be possible to obtain polycyclic structures with up to four stereogenic centers. The choice of catalyst will be of great importance to enable processes with a high degree of stereoselectivity

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