@article{yu_tang_cha_milikisiyants_smirnova_smirnov_guo_chang_2018, title={Elucidating the Reaction Pathway of Decarboxylation-Assisted Olefination Catalyzed by a Mononuclear Non-Heme Iron Enzyme}, volume={140}, ISSN={["1520-5126"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85056414780&partnerID=MN8TOARS}, DOI={10.1021/jacs.8b10077}, abstractNote={Installation of olefins into molecules is a key transformation in organic synthesis. The recently discovered decarboxylation-assisted olefination in the biosynthesis of rhabduscin by a mononuclear non-heme iron enzyme ( P.IsnB) represents a novel approach in olefin construction. This method is commonly employed in natural product biosynthesis. Herein, we demonstrate that a ferryl intermediate is used for C-H activation at the benzylic position of the substrate. We further establish that P.IsnB reactivity can be switched from olefination to hydroxylation using electron-withdrawing groups appended on the phenyl moiety of the analogues. These experimental observations imply that a pathway involving an initial C-H activation followed by a benzylic carbocation species or by electron transfer coupled β-scission is likely utilized to complete C═C bond formation.}, number={45}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Yu, Cheng-Ping and Tang, Yijie and Cha, Lide and Milikisiyants, Sergey and Smirnova, Tatyana I. and Smirnov, Alex I. and Guo, Yisong and Chang, Wei-chen}, year={2018}, month={Nov}, pages={15190–15193} }
 @article{huang_tang_yu_sanyal_jia_liu_guo_chang_2018, title={Mechanistic Investigation of Oxidative Decarboxylation Catalyzed by Two Iron(II)- and 2-Oxoglutarate-Dependent Enzymes}, volume={57}, ISSN={["0006-2960"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85044655678&partnerID=MN8TOARS}, DOI={10.1021/acs.biochem.8b00115}, abstractNote={Two non-heme iron enzymes, IsnB and AmbI3, catalyze a novel decarboxylation-assisted olefination to produce indole vinyl isonitrile, an important building block for many natural products. Compared to other reactions catalyzed by this enzyme family, decarboxylation-assisted olefination represents an attractive biosynthetic route and a mechanistically unexplored pathway in constructing a C═C bond. Using mechanistic probes, transient state kinetics, reactive intermediate trapping, spectroscopic characterizations, and product analysis, we propose that both IsnB and AmbI3 initiate stereoselective olefination via a benzylic C-H bond activation by an Fe(IV)-oxo intermediate, and the reaction likely proceeds through a radical- or carbocation-induced decarboxylation to complete C═C bond installation.}, number={12}, journal={BIOCHEMISTRY}, author={Huang, Jhih-Liang and Tang, Yijie and Yu, Cheng-Ping and Sanyal, Dev and Jia, Xinglin and Liu, Xinyu and Guo, Yisong and Chang, Wei-chen}, year={2018}, month={Mar}, pages={1838–1841} }