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´
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reacts with copper species to afford copper-carbenoid I. Generation
of a copper-carbenoid species was evidenced by the observation that
a dimeric mixture of diazoacetate was formed as a byproduct19 when
a deoxygenation was not efficiently occurred (Scheme 5). Subsequent
attack at the electrophilic carbene carbon by the oxygen atom of
quinoline N-oxide generates an oxonium ylide II. It is believed that
the decomposition of intermediate II will take place as the final step
to afford methyl benzoylformate and deoxygenated product.
In conclusion, the deoxygenation of N-oxides including both
heterocyclic and alkyl(aryl)amine derivatives has been successfully
developed by the copper-catalyzed oxygen atom transfer using diazo
compounds as the oxygen atom acceptor. The reaction was highly
mild, efficient, and chemoselective to allow for high functional
group tolerance. As proved by the convenient one-pot synthesis of
8-functionalized quinoline from quinoline, this new method is
anticipated to be highly useful especially when it is combined with
the direct C–H functionalization of heterocyclic compounds.
This research was supported by the Institute for Basic
Science (IBS-R010-D1).
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7038 | Chem. Commun., 2015, 51, 7035--7038
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