Overview on Multienzymatic Cascades for the Production of Non-canonical α-Amino Acids

SM-R thanks the University of Granada for the support provided by project PPJI2017-1 and the European Cooperation in Science and Technology (COST Action CA15133). Authors are also grateful to the Andalusian Regional Government through Endocrinology & Metabolism Group (CTS-202).The 22 genetically encoded amino acids (AAs) present in proteins (the 20 standard AAs together with selenocysteine and pyrrolysine), are commonly referred as proteinogenic AAs in the literature due to their appearance in ribosome-synthetized polypeptides. Beyond the borders of this key set of compounds, the rest of AAs are generally named imprecisely as non-proteinogenic AAs, even when they can also appear in polypeptide chains as a result of post-transductional machinery. Besides their importance as metabolites in life, many of D-α- and L-α-“non-canonical” amino acids (NcAAs) are of interest in the biotechnological and biomedical fields. They have found numerous applications in the discovery of new medicines and antibiotics, drug synthesis, cosmetic, and nutritional compounds, or in the improvement of protein and peptide pharmaceuticals. In addition to the numerous studies dealing with the asymmetric synthesis of NcAAs, many different enzymatic pathways have been reported in the literature allowing for the biosynthesis of NcAAs. Due to the huge heterogeneity of this group of molecules, this review is devoted to provide an overview on different established multienzymatic cascades for the production of non-canonical D-α- and L-α-AAs, supplying neophyte and experienced professionals in this field with different illustrative examples in the literature. Whereas the discovery of new or newly designed enzymes is of great interest, dusting off previous enzymatic methodologies by a “back and to the future” strategy might accelerate the implementation of new or improved multienzymatic cascades.University of Granada PPJI2017-1European Cooperation in Science and Technology (COST) CA15133Andalusian Regional Government through Endocrinology & Metabolism Group CTS-20

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