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Iron-Catalyzed C—H Insertions: Organometallic and Enzymatic Carbene Transfer Reactions

preprint
submitted on 21.03.2018 and posted on 21.03.2018 by Katharina J. Hock, Anja Knorrscheidt, Renè Hommelsheim, Junming Ho, Martin J. Weissenborn, Rene M. Koenigs

C—H insertion reactions with organometallic and enzymatic catalysts based on earth-abundant iron complexes remain one of the major challenges in organic synthesis. In this report, we describe the development and application of these iron-based catalysts in the reaction of two different carbene precursors with N-heterocycles for the first time. While FeTPPCl showed excellent reactivity in the Fe(III) state with diazoacetonitrile, the highest activities of the YfeX enzyme could be achieved upon heme-iron reduction to Fe(II) with both diazoacetonitrile and ethyl diazoacetate. This highlights unexpected and subtle differences in reactivity of both iron catalysts. Deuterium labeling studies indicated a C—H insertion pathway and a marked kinetic isotope effect. This transformation features mild reaction conditions, excellent yields or turnover numbers with broad functional group tolerance, including gram-scale applications giving a unique access to functionalized N-heterocycles.

History

Email Address of Submitting Author

rene.koenigs@rwth-aachen.de

Email Address(es) for Other Author(s)

katharina.hock@rwth-aachen.de Anja.Knorrscheidt@ipb-halle.de rene.hommelsheim@rwth-aachen.de junming.ho@unsw.edu.au martin.weissenborn@ipb-halle.de

Institution

RWTH Aachen University, Institute of Organic Chemistry

Country

Germany

ORCID For Submitting Author

0000-0003-0247-4384

Declaration of Conflict of Interest

The authors declare no conflict of interest.

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