The overall enthalpic barriers for 1a-g to RCD are high, which is anticipated for an uncatalyzed transformation. In a previously reported kinetic study, the DBU catalyzed RCD of an aliphatic polycarbonate (based on the monomer S1c, Supplementary Fig. ) in MeCN was observed to have a kapp = 6.4 x 10 -4 s -1 corresponding approximately to a ∆G ‡ of 26.1 kcal/mol. This value is roughly half of the enthalpic barriers computed for 1a-g via DFT or DFTB in MeCN, which of course may still vary significantly in total energy depending on the entropic contributions. The stark difference between these values highlights the critical role of catalysts in facilitating the RCD transformation in solution as well as the kinetic trapping of these systems in the polymeric state. Nonetheless, as noted above, useful trends can be observed in the relative changes of the enthalpic barrier as a function of different conditions. Given the height of the enthalpic barrier, we opted to verify experimentally the uncatalyzed thermal depolymerization of the corresponding polymers of 1c and 1d under neat conditions. Here, the RCD at 230 °C for 12 h gave M1c and M1d in approximately 67% and 63% conversion, respectively, as determined by relative ratios of their NMR peaks (Supplementary Fig. ). Having evaluated the trends of the enthalpic barriers for carbonates 1a-g, we next sought to determine whether these would prove generalizable to a much broader set of potential aliphatic carbonate systems with very different types of functional groups. As noted in the Methods section, the selection protocol used for identifying 2a-ar (Supplementary Fig. ) specifically targeted molecules containing Mordred features not present in the 1a-g. However, this method did not evenly cover all groups of molecules within the search space, based on the low-dimensional representation (Fig. ). Comparison the correlation of Mordred features to the DFTB-computed energy barrier shows a dramatic variation between features shared by the two datasets (Fig. ). Additionally, the most strongly correlated feature from 2a-ar is the number of hydrogen bond donors (0.47), which is much lower than the most strongly correlated features from 1a-g (Fig. ). Additionally, while some of the monomers from the expanded 2a-ar dataset contain examples of systems that have potentially reactive pendant functional groups (for example, 2d and 2e, Supplementary Fig. ) that may interfere with RCD under experimental evaluation, it is still illustrative to include them as part of examining broader trends across a diversity of carbonate systems.