Hyperspace exploration using robotics for the discovery of mechanistically distinct transformations and complex functional products

Chemical reactions are traditionally viewed as linear transformations, yet in reality they unfold as mechanistic networks embedded within multidimensional ‘hyperspaces’ of conditions. Systematic exploration of these spaces can redirect classical reactions into unexpected branches representing new reactivity patterns. Here we report the discovery of a pseudo-seven-component transformation within the hyperspace of the century-old Biginelli reaction, yielding polycyclic products with substantial structural and stereochemical complexity. These products also exhibit rare supramolecular behaviours, from hierarchical assembly to metal-programmed chiral sorting. Together, these findings demonstrate that hyperspace exploration can uncover mechanistically distinct and functionally useful reactions, expanding the boundaries of chemical reactivity. The hyperspace of reaction conditions of the Biginelli reaction is scanned using a robotic platform, revealing a pseudo-seven-component transformation that yields a bicyclic product featuring rare supramolecular behaviour. This work shows that the chemical reaction is a switchable network embedded within a hyperspace of conditions, rather than a linear transformation.