Biocatalysis: landmark discoveries and applications in chemical synthesis

Abstract

This tutorial review will give readers an insight into the landmark discoveries and milestones that have helped shape and grow the field of biocatalysis since the discovery of the first enzyme.

Chemogenetic Evolution of Diversified Photoenzymes for Enantioselective [2 + 2] Cycloadditions in Whole Cells

“…Furthermore, 10 mg-scale biotransformation was performed for the model substrate, and comparable results were obtained (95% yield, 96:4 e.r., Figure 4). 1 H and 13 C NMR of isolated product 2a were identical to that obtained using racemic standard (Figure S15). The absolute stereochemistry of photoadducts was assigned by analogy to compound 2d, whose structure was unambiguously elucidated through X-ray crystallography (Figure S16 and Table S16).…”

“…The three-dimensional supramolecular chiral cavity of proteins provides a delicate and hierarchical microenvironment for precisely controlling selectivities in challenging organic reactions. − This advantage becomes particularly evident when handling transient and fleeting radical intermediates in photocatalysis, a task often challenging for chiral small molecule catalysts due to their high reactivity and free diffusion properties. , Photoenzymes present a promising solution to address this challenge as they can be precisely tailored through rational design and directed evolution to create a tailored chiral pocket for accommodating substrates with high enantioinduction. − The capability of photoenzymes has been demonstrated in a variety of enantioselective transformations such as radical reduction, cyclization, conjugated addition, and cross-coupling, − primarily leveraging the photophysical properties of natural cofactors such as flavin or nicotinamides. Recently, the Green group and we simultaneously reported genetically encoded artificial photoenzymes incorporating a non-natural amino acid (nnAA), i.e., 4-benzoylphenylalanine (BpA).…”