Mechanism of radical initiation in the radical SAM enzyme superfamily

BM Hoffman, WE Broderick… - Annual review of …, 2023 - annualreviews.org
Radical S-adenosylmethionine (SAM) enzymes use a site-differentiated [4Fe-4S] cluster and
SAM to initiate radical reactions through liberation of the 5′-deoxyadenosyl (5′-dAdo•) …

Radical SAM enzymes: nature's choice for radical reactions

JB Broderick, WE Broderick, BM Hoffman - FEBS letters, 2023 - Wiley Online Library
Enzymes that use a [4Fe‐4S] 1+ cluster plus S‐adenosyl‐l‐methionine (SAM) to initiate
radical reactions (radical SAM) form the largest enzyme superfamily, with over half a million …

Biosynthesis of 3-thia-α-amino acids on a carrier peptide

Y Yu, WA van der Donk - Proceedings of the National …, 2022 - National Acad Sciences
A subset of natural products, such as polyketides and nonribosomal peptides, is
biosynthesized while tethered to a carrier peptide via a thioester linkage. Recently, we …

Pyruvate formate-lyase activating enzyme: The catalytically active 5′-deoxyadenosyl radical caught in the act of H-atom abstraction

MN Lundahl, H Yang, WE Broderick… - Proceedings of the …, 2023 - National Acad Sciences
Enzymes of the radical S-adenosyl-l-methionine (radical SAM, RS) superfamily, the largest
in nature, catalyze remarkably diverse reactions initiated by H-atom abstraction. Glycyl …

Improved production of class I lanthipeptides in Escherichia coli

H Lee, C Wu, EK Desormeaux, R Sarksian… - Chemical …, 2023 - pubs.rsc.org
Lanthipeptides are ribosomally synthesised and post-translationally modified peptides
containing lanthionine (Lan) and methyllanthionine (MeLan) residues that are formed by …

Computational Description of Alkylated Iron–Sulfur Organometallic Clusters

RJ Jodts, M Wittkop, MB Ho, WE Broderick… - Journal of the …, 2023 - ACS Publications
The radical S-adenosyl methionine (SAM) enzyme superfamily has widespread roles in
hydrogen atom abstraction reactions of crucial biological importance. In these enzymes …

Reversible Alkyl-Group Migration between Iron and Sulfur in [Fe4S4] Clusters

M Ye, AC Brown, DLM Suess - Journal of the American Chemical …, 2022 - ACS Publications
Synthetic [Fe4S4] clusters with Fe–R groups (R= alkyl/benzyl) are shown to release organic
radicals on an [Fe4S4] 3+–R/[Fe4S4] 2+ redox couple, the same that has been proposed for …

Direct Detection of the α-Carbon Radical Intermediate Formed by OspD: Mechanistic Insights into Radical S-Adenosyl-l-methionine Peptide Epimerization

WG Walls, AL Vagstad, T Delridge, J Piel… - Journal of the …, 2024 - ACS Publications
OspD is a radical S-adenosyl-l-methionine (SAM) peptide epimerase that converts an
isoleucine (Ile) and valine (Val) of the OspA substrate to d-amino acids during biosynthesis …

Characterization by ENDOR spectroscopy of the iron–alkyl bond in a synthetic counterpart of organometallic intermediates in radical SAM enzymes

MB Ho, RJ Jodts, Y Kim, A McSkimming… - Journal of the …, 2022 - ACS Publications
Members of the radical S-adenosyl-l-methionine (SAM) enzyme superfamily initiate a broad
spectrum of radical transformations through reductive cleavage of SAM by a [4Fe–4S] 1+ …

Changing Fates of the Substrate Radicals Generated in the Active Sites of the B12-Dependent Radical SAM Enzymes OxsB and AlsB

YH Lee, YC Yeh, PH Fan, A Zhong… - Journal of the …, 2023 - ACS Publications
OxsB is a B12-dependent radical SAM enzyme that catalyzes the oxidative ring contraction
of 2′-deoxyadenosine 5′-phosphate to the dehydrogenated, oxetane containing …