Fast biomass pyrolysis has been heavily investigated as a potential source of inexpensive chemicals and sustainable energy. D-Glucose is a biomass feedstock that has gained wide interest for decades because it is readily available from cellulose and exhibits high selectivity in producing furan products. However, resolving the reaction pathways for glucose pyrolysis is challenging because of the multi-step nature of plausible mechanisms and the likelihood of competing reactions. Due to this complexity, even computational studies of glucose pyrolysis pathways have focused on a handful of curated reaction classes or hypothesis-driven mechanisms. For example, many have focused on identifying the dominant pathways for forming hydroxymethylfurfural (HMF) from glucose using a series of β-elimination and isomerization reactions. However, the activation energies of the proposed pathways to HMF formation are still relatively high (∼ 60 kcal/mol), and do not provide convincing explanations for higher yields of HMF compared to other products, such as hydroxyacetaldehyde (HAA).