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Abstract
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.
Supplementary materials
Title
Dydioetal-SI1
Description
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