Radical Breakthroughs in Natural Product and Cofactor Biosynthesis.

Biochemistry
Kenichi Yokoyama

Abstract

The radical SAM (S-adenosyl-l-methionine) superfamily is one of the largest group of enzymes with >113000 annotated sequences [Landgraf, B. J., et al. (2016) Annu. Rev. Biochem. 85, 485-514]. Members of this superfamily catalyze the reductive cleavage of SAM using an oxygen sensitive 4Fe-4S cluster to transiently generate 5'-deoxyadenosyl radical that is subsequently used to initiate diverse free radical-mediated reactions. Because of the unique reactivity of free radicals, radical SAM enzymes frequently catalyze chemically challenging reactions critical for the biosynthesis of unique structures of cofactors and natural products. In this Perspective, I will discuss the impact of characterizing novel functions in radical SAM enzymes on our understanding of biosynthetic pathways and use two recent examples from my own group with a particular emphasis on two radical SAM enzymes that are responsible for carbon skeleton formation during the biosynthesis of a cofactor and natural products.

References

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May 6, 2015·Proceedings of the National Academy of Sciences of the United States of America·Bradley M HoverKenichi Yokoyama
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Citations

Feb 28, 2018·Natural Product Reports·Mark W RuszczyckyHung-Wen Liu
Jun 23, 2018·Chemical Reviews·F Peter Guengerich, Francis K Yoshimoto
Oct 6, 2020·Biochimica Et Biophysica Acta. Molecular Cell Research·Simon J MayrGuenter Schwarz

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