Four Simultaneously Dynamic Covalent Reactions. Experimental Proof of Orthogonality.

Dynamic covalent reactions are widely used in dynamic combinatorial chemistry. Most of these reactions are run under differing reaction conditions and exhibit cross-reactivity when components of multiple reactions are present in one reaction vessel. Herein, we report the study of four dynamic covalent reactions that react reversibly under identical reaction conditions and do not exhibit any cross-reactivity. Dynamic behavior was shown via (1)H NMR based exchange experiments. Computational deconvolution of (1)H NMR spectra containing the components for more than one of the orthogonal reactions allowed for a semiquantitative analysis of the complex mixtures formed, showing that the reactions proceed independently of each other. Therefore, it is possible to use all four reactions in one pot in a simultaneous, yet orthogonal fashion. This opens up possibilities for the preprogrammed formation of complex thermodynamic assemblies.