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Studying the Outcomes and Mechanisms of Carbocationic Rearrangements Using Algorithm‐Augmented Experimentation

Year: 2025

Type: article

Abstract: Carbocationic rearrangements are fundamental to both biosynthetic and synthetic chemistries, yet their high reactivity and mechanistic complexity often defy intuitive prediction of outcomes. Herein, HopCat, a hybrid algorithmic platform combining rule‐based transformation logic with quantum‐mechanically informed kinetics, is applied to explore the rearrangement networks of acid‐catalyzed terpenoid transformations. Using a series of terpenoid substrates, an array of structurally diverse and unprecedented products is obtained. It is narated how HopCat can work synergistically with a human chemist to guide product assignment, downselect product candidates based on NMR cues, and reconstruct plausible, multistep mechanistic pathways, including those involving unanticipated intermediates.

Source: ChemistryEurope

DOI: 10.1002/ceur.202500189