The study identified and structurally characterized four previously unknown oxidized products of T5αH through 1D and 2D NMR spectroscopy. The characterization of these novel products, such as 5,11-ether and other complex taxadiene rearrangements, provided new insights into the potential intermediates and shunt pathways in paclitaxel biosynthesis. These products include di-oxidized and tri-oxidized taxadienes, which were hypothesized to arise from over-oxidation by T5αH. These findings are important for understanding the bottlenecks and side-reactions in heterologous systems.