S ‐Adenosyl‐ l ‐ethionine is a Catalytically Competent Analog of S ‐Adenosyl‐ l ‐methionine (SAM) in the Radical SAM Enzyme HydG

Impano, Stella; Yang, Hao; Shepard, Eric M.; Swimley, Ryan; Pagnier, Adrien; Broderick, William E.; Hoffman, Brian M.; Broderick, Joan B.

doi:10.1002/ange.202014337

Title: S ‐Adenosyl‐ l ‐ethionine is a Catalytically Competent Analog of S ‐Adenosyl‐ l ‐methionine (SAM) in the Radical SAM Enzyme HydG

Journal Article · Mon Jan 18 00:00:00 EST 2021 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202014337· OSTI ID:1786119

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Department of Chemistry &, Biochemistry Montana State University Bozeman MT 59717 USA
Department of Chemistry Northwestern University Evanston IL 60208 USA

Abstract Radical S ‐adenosyl‐ l ‐methionine (SAM) enzymes initiate biological radical reactions with the 5′‐deoxyadenosyl radical (5′‐dAdo ^. ). A [4Fe‐4S] ⁺ cluster reductively cleaves SAM to form the Ω organometallic intermediate in which the 5′‐deoxyadenosyl moiety is directly bound to the unique iron of the [4Fe‐4S] cluster, with subsequent liberation of 5′‐dAdo ^. . We present synthesis of the SAM analog S ‐adenosyl‐ l ‐ethionine (SAE) and show SAE is a mechanistically equivalent SAM‐alternative for HydG, both supporting enzymatic turnover of substrate tyrosine and forming the organometallic intermediate Ω. Photolysis of SAE‐bound HydG forms an ethyl radical trapped in the active site. The ethyl radical withstands prolonged storage at 77 K and its EPR signal is only partially lost upon annealing at 100 K, making it significantly less reactive than the methyl radical formed by SAM photolysis. Upon annealing above 77 K, the ethyl radical adds to the [4Fe‐4S] ²⁺ cluster, generating an ethyl‐[4Fe‐4S] ³⁺ organometallic species termed Ω _E .

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Sponsoring Organization:: USDOE

OSTI ID:: 1786119

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 133 Journal Issue: 9; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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