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Dual-Catalytic Transition Metal Systems for Functionalization of Unreactive Sites of Molecules

submitted on 22.10.2018 and posted on 23.10.2018 by Dawid Lichosyt, Yang Zhang, Karolina Hurej, Pawel Dydio
Catalytic reactions occur readily at sites of starting materials that are both innately reactive and sterically accessible or that are predisposed by a functional group amenable to direct a catalyst. However, selective reactions at unbiased sites of substrates remain challenging and typically require additional pre-activation steps or the use of highly reactive reagents. Herein, we report dual-catalytic transition metal systems that merge a reversible activation cycle with a functionalization cycle, together enabling functionalization of substrates at their inherently unreactive sites. By engaging the Ru- or Fe-catalyzed equilibrium between an alcohol and an aldehyde, Pd-catalyzed b-arylation of aliphatic alcohols and Rh-catalyzed g-hydroarylation of allylic alcohols were developed. The mild conditions, functional group tolerance and broad scope of the methodologies (81 examples) demonstrate the synthetic applicability of the dual-catalytic systems. In a broader context, this work highlights the potential of the multi-catalytic approach to address challenging transformations to circumvent the multi-step procedures and the use of highly reactive reagents in organic synthesis.


Email Address of Submitting Author


University of Strasbourg, CNRS, ISIS UMR 7006, F-67000 Strasbourg, France



ORCID For Submitting Author


Declaration of Conflict of Interest

The authors declare no conflict of interest.