Premium
Expanding Radical SAM Chemistry by Using Radical Addition Reactions and SAM Analogues
Author(s) -
Ji Xinjian,
Li Yongzhen,
Xie Liqi,
Lu Haojie,
Ding Wei,
Zhang Qi
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201605917
Subject(s) - chemistry , moiety , hydrogen atom abstraction , radical , adduct , radical ion , olefin fiber , nucleoside , substrate (aquarium) , combinatorial chemistry , photochemistry , stereochemistry , organic chemistry , catalysis , ion , oceanography , geology
Radical S ‐adenosyl‐ l ‐methionine (SAM) enzymes utilize a [4Fe‐4S] cluster to bind SAM and reductively cleave its carbon–sulfur bond to produce a highly reactive 5′‐deoxyadenosyl (dAdo) radical. In almost all cases, the dAdo radical abstracts a hydrogen atom from the substrates or from enzymes, thereby initiating a highly diverse array of reactions. Herein, we report a change of the dAdo radical‐based chemistry from hydrogen abstraction to radical addition in the reaction of the radical SAM enzyme NosL. This change was achieved by using a substrate analogue containing an olefin moiety. We also showed that two SAM analogues containing different nucleoside functionalities initiate the radical‐based reactions with high efficiencies. The radical adduct with the olefin produced in the reaction was found to undergo two divergent reactions, and the mechanistic insights into this process were investigated in detail. Our study demonstrates a promising strategy in expanding radical SAM chemistry, providing an effective way to access nucleoside‐containing compounds by using radical SAM‐dependent reactions.