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submitted on 22.10.2018 and posted on 23.10.2018by 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
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.