Enzyme‐Triggered Reactions for the Synthesis of Organic Molecules

Abstract

The application of enzymes for the synthesis of valuable bioactive molecules, synthetic building blocks, fine chemicals and natural products is now well‐established. Biocatalysis has been embraced by industry for the preparation of both bulk chemicals and active pharmaceutical ingredients, where high activity and selectivity can be achieved with low environmental impact. In most cases, biocatalytic transformations involve functional group interconversions, such as redox and amination reactions, but do not lead to significant complexity generation in the molecule. This review explores the less prevalent enzyme‐triggered reactions, where the enzymatic transformation triggers a subsequent spontaneous reaction inter/intramolecularly. The examples highlighted in this review showcase the synthetic power of designing smart substrates for enzyme‐triggered reactions and their application for the preparation of structurally complex three‐dimensional small molecules.