Emergent Mechanisms in Biocatalysis.

Enzymes are invaluable tools for solving challenges in synthetic organic chemistry. Beyond replicating native reactivity patterns, modern directed evolution strategies have enabled chemists to efficiently survey chemical space to identify enzyme families capable of catalyzing non-natural reactions. While methods often focus on chemo-, enantio-, and regiocontrol, there are a growing number of examples that describe reactivity patterns and reaction mechanisms that were previously unknown in the synthetic literature. In this Perspective, we will explore examples of such emergent mechanistic pathways of enzymes in the context of synthetic precedents, emphasizing the remarkable versatility of diverse enzyme active sites in controlling unprecedented transformations.