Unravelling a fulvene based Replicator: Experiment and Theory in Interplay

A self-replicating system based on a cycloaddition of a fulvene derivative and a maleinimide is investigated using a two-pronged approach combining NMR spectroscopy with computer simulations. In the course of the reaction, two diastereomers are formed with identical rates in the absence of replication. When replication is enabled, a network emerges in which one diastereomer takes over the resources as a "selfish" autocatalyst while exploiting the competitor as a weak "altruist". The structure and dynamics of the reaction network is studied using 1 D and 2 D NMR techniques supported by dynamically averaged ab initio chemical shifts and ab initio molecular dynamics simulations. It is shown that this combination is a powerful means to understand the observed experimental behaviour in great detail.