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CC BY-NC-ND 4.0 · Synthesis 2021; 53(15): 2583-2593
DOI: 10.1055/a-1458-2419
short review

Molecular Editing of Flavins for Catalysis

Andreas Rehpenn‡
,
Alexandra Walter‡
,
Golo Storch  ∗
The Fonds der Chemischen Industrie (FCI, Ph.D. Fellowship to A.W. and Liebig Fellowship to G.S.) is gratefully acknowledged. Our group is supported by the Technische Universität München through the Junior Fellow Programme.
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Abstract

The diverse activity of flavoenzymes in organic transformations has fascinated researchers for a long time. However, when applied outside an enzyme environment, the isolated flavin cofactor only shows largely reduced activity. This highlights the importance of embedding the reactive isoalloxazine core of flavins in defined surroundings. The latter include crucial non-covalent interactions with amino acid side chains or backbone as well as controlled access to reactants such as molecular oxygen. Nevertheless, molecular flavins are increasingly applied in the organic laboratory as valuable organocatalysts. Chemical modification of the parent isoalloxazine structure is of particular interest in this context in order to achieve reactivity and selectivity in transformations, which are so far only known with flavoenzymes or even unprecedented. This review aims to give a systematic overview of the reported designed flavin catalysts and highlights the impact of each structural alteration. It is intended to serve as a source of information when comparing the performance of known catalysts, but also when designing new flavins. Over the last few decades, molecular flavin catalysis has emerged from proof-of-concept reactions to increasingly sophisticated transformations. This stimulates anticipating new flavin catalyst designs for solving contemporary challenges in organic synthesis.

1 Introduction

2 N1-Modification

3 N3-Modification

4 N5-Modification

5 C6–C9-Modification

6 N10-Modification

7 Conclusion

Key words

flavin catalysis - organic synthesis - biomimetic chemistry - organocatalysis


Publication History

Received: 14 February 2021

Accepted after revision: 22 March 2021

Accepted Manuscript online:
22 March 2021

Article published online:
26 April 2021

© 2021. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial-License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)

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