We have here presented the first large-scale automated multiconfigurational approach to the modeling of organic reactivity, which provides a compelling alternative to DFT and CCSD(T) for interrogating chemical space. These multiconfigurational methods have been held back from high-throughput application for decades due to the problem of active space inconsistency error (ASIE), which is here overcome through the increased robustness of the MC-PDFT method to ASIE and automated active space selection with the approximate pair coefficient (APC) approach. We have applied this automated APC-PDFT approach to the calculation of 908 main group reactions from the RGD1 database, which successfully reproduces the single-reference limit with ASIE of ±2.2 kcal/mol (similar to deviations between different density functionals) while providing more accurate multiconfigurational descriptions than DFT and CCSD(T) in many of the 68% of reactions containing multiconfigurational character. Taken at face value, these results make it possible to for the first time envision the high-throughput use of multiconfigurational methods in this domain, potentially increasing the accuracy of predictions at significantly lower cost (and possibly higher accuracy) than CCSD(T).