30685-66-6Relevant articles and documents
Sulfonium-Based Homolytic Substitution Observed for the Radical SAM Enzyme HemN
Deng, Zixin,Ding, Wei,Ji, Wenjuan,Ji, Xinjian,Mandalapu, Dhanaraju,Sun, Peng,Zhang, Qi
supporting information, p. 8880 - 8884 (2020/04/01)
Sulfur-based homolytic substitution (SH reaction) plays an important role in synthetic chemistry, yet whether such a reaction could occur on the positively charged sulfonium compounds remains unknown. In the study of the anaerobic coproporphyrinogen III oxidase HemN, a radical S-adenosyl-l-methionine (SAM) enzyme involved in heme biosynthesis, we observed the production of di-(5′-deoxyadenosyl)methylsulfonium, which supports a deoxyadenosyl (dAdo) radical-mediated SH reaction on the sulfonium center of SAM. The sulfonium-based SH reactions were then investigated in detail by density functional theory calculations and model reactions, which showed that this type of reactions is thermodynamically favorable and kinetically competent. These findings represent the first report of sulfonium-based SH reactions, which could be useful in synthetic chemistry. Our study also demonstrates the remarkable catalytic promiscuity of the radical SAM superfamily enzymes.
Synthetic Approaches towards Nucleocidin and Selected Analogues; anti-HIV Activity in 4'-Fluorinated Nucleoside Derivatives
Maguire, Anita R.,Meng, Wei-dong,Roberts, Stanley M.,Willetts, Andrew J.
, p. 1795 - 1808 (2007/10/02)
Nucleocidin 1 has been synthesised from the adenosine derivative 4 via the intermediacy of the dihalogeno compound 9.The latter compound showed slight but significant activity against HIV-infected cells while the isomer 10 and the monohalogeno compound 60 were inactive.Synthetic approaches towards other 4'-fluorinated nucleoside derivatives are also described.The epimeric 4'-fluorinated nucleosides 26 and 27 displayed similar activity against HIV-infected cells to that observed for the dihalogenated compound 9.