Selective methylene
C–H oxidation for the synthesis of alcohols
with a broad scope and functional group tolerance is challenging due
to the high proclivity for further oxidation of alcohols to ketones.
Here, we report the selective synthesis of benzylic alcohols employing
bis(methanesulfonyl) peroxide as an oxidant. We attempt to provide
a rationale for the selectivity for monooxygenation, which is distinct
from previous work; a proton-coupled electron transfer mechanism (PCET)
may account for the difference in reactivity. We envision that our
method will be useful for applications in the discovery of drugs and
agrochemicals.
Synthetic methods for oxidative aromatic C−O bond formation are sparse, despite their demand in metabolite synthesis for drug discovery and development. We report a novel methodology for late-stage C−O bond formation of arenes. The reaction proceeds with excellent functional group tolerance even for highly functionalized substrates. The resulting aryl mesylates provide access to potential human metabolites of pharmaceuticals, and may be used directly to install a C−F bond to block metabolic hotspots. A charge-transfer interaction between the reagent bis(methanesulfonyl) peroxide and the substrate arenes may be relevant for the chemoselective functionalization of arenes over other functional groups.
Iodoarenes are versatile
intermediates and common synthetic targets
in organic synthesis. Here, we present a strategy for selective C–H
iodination of (hetero)arenes with a broad functional group tolerance.
We demonstrate the utility and differentiation to other iodination
methods of supposed sulfonyl hypoiodites for a set of carboarenes
and heteroarenes.
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