4
mechanism for the alcohol oxidation is illustrated in the Scheme 3.
Initially, the reagent CBI dissociates into hypochlorous acid and 2-
iodobenzoic acid in the presence of water. Subsequently, TEMPO is
converted to oxoammonium salt by the hypochlorous acid. This
oxoammonium salt oxidizes the alcohol through hydride transfer
mechanism to yield the aldehyde and intermediate B. The resulted
aldehyde undergoes formation of gem-diol in the presence of water
and gets oxidized to corresponding carboxylic acid by the
J. K. gratefully acknowledges DST-India for young scientist start-up
research grant (YSS/2014/000236). A. K. S acknowledges CSIR for
junior research fellowship (JRF). J. K. thanks Central
Instrumentation Facility Centre (CIFC)-IIT BHU for the NMR
facilities.
References
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The second equivalent of oxoammonium salt is generated by the
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Scheme 2. Oxidation of aldehyde using CBI in the absence of
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Scheme 3. Plausible mechanism for the alcohol oxidation.
In summary, a highly efficient TEMPO-catalysed alcohol oxidation
protocol is developed using 1-chloro-1,2-benziodoxol-3(1H)-one as
the terminal oxidant. This protocol provides various uronic acids in
excellent yields from corresponding alcohols under mild reaction
conditions. Moreover, primary alcohols were selectively oxidized
over the secondary alcohols making this protocol potentially useful
in the complex oligosaccharide synthesis.
(7)
Acknowledgements: