Derivatives of Natural Organocatalytic Cofactors and Artificial Organocatalytic Cofactors as Catalysts in Enzymes

Abstract

Catalytically active non-metal cofactors in enzymes carry out a variety of different reactions. The efforts to develop derivatives of naturally occurring cofactors such as flavins or pyridoxal phosphate and the advances to design new, non-natural cofactors are reviewed here. We report the status quo for enzymes harboring organocatalysts as derivatives of natural cofactors or as artificial ones and their application in the asymmetric synthesis of various compounds.

Going Full Circle with Organocatalysis and Biocatalysis: The Latent Potential of Cofactor Mimics in Asymmetric Synthesis

“…Instead, organocatalysis has taken advantage of the very tight binding within biotin–streptavidin complexes to introduce enzyme-like control on the outcomes of different organocatalytic reactions. Several transformations have been explored, including iminium ion catalysis in the reaction of cinnamaldehyde with nitromethane, enamine-catalyzed aldol reactions, anion−π catalysis, and organocatalytic transfer hydrogenations, which have been reviewed . The supramolecular streptavidin host, with inherent asymmetry, imparts good diastereo- and enantioselectivities.…”

“…Our synopsis is directed particularly toward chemists with an emphasis on asymmetric catalysis in line with the focus of the special issue. An excellent recent review in 2022 by Lechner and Oberdorfer, also on cofactor catalysis, covers complementary examples …”

“…An excellent recent review in 2022 by Lechner and Oberdorfer, also on cofactor catalysis, covers complementary examples. 16 Looking to the future, synergistic approaches combining the fundamental knowledge developed in both bio-and organocatalysis could unveil new areas of asymmetric chemistry, particularly through the introduction of non-native cofactors to biocatalytic transformations to enhance reactivity and scope.…”

“…An excellent recent review in 2022 by Lechner and Oberdorfer, also on cofactor catalysis, covers complementary examples. 16 …”

Alkyne Oxidation by a Vitamin B2-Based Photocatalytic System with Both H2O and O2 as the Oxygen Source

“…Riboflavin (RF), also known as vitamin B2, belongs to flavin (Fl) coenzyme and is a small organic molecule that participates in various biological photoredox reactions . In chemistry, RF and its most widely used derivative, the acetylated vitamin B2 (riboflavin tetraacetate, RFT, Scheme b), have been used as photocatalysts in two-electron oxidation and recently one-electron oxidation in the presence of O 2 .…”