ORGANIC
LETTERS
2011
Vol. 13, No. 24
6488–6491
Design, Synthesis, Structure, and
Dehydrogenation Reactivity of a Water-
Soluble o-Iodoxybenzoic Acid Derivative
Bearing a Trimethylammonium Group
Li-Qian Cui, Zhi-Lei Dong, Kai Liu, and Chi Zhang*
State Key Laboratory of Elemento-Organic Chemistry, Research Institute of Elemento
Organic Chemistry, Nankai University, Tianjin 300071, China
Received October 15, 2011
ABSTRACT
5-Trimethylammonio-1,3-dioxo-1,3-dihydro-1λ5-benzo[d][1,2]iodoxol-1-ol anion (AIBX 1a), an o-iodoxybenzoic acid (IBX) derivative having the
trimethylammonium moiety on its phenyl ring, possesses very good solubility in water and distinct oxidative properties from IBX, which is
demonstrated in the oxidation of various β-keto esters to the corresponding dehydrogenated products using water as cosolvent. The regeneration
of AIBX 1a can be easily realized from the reaction mixture due to its good water solubility.
IBX (Figure 1), a key representative of organo-penta-
valent iodine reagents, has found widespread applications
in organic synthesis as a mild and nontoxic oxidizing
agent.1 In most cases, the solvent of IBX mediated reac-
tions is DMSO due to the insolubility of IBX in other
common organic solvents, which is a major drawback
of IBX to restrict its practical application. IBX has also
been reported to be explosive upon impact or excessive
heating.2 To overcome its solubility limitation, a few IBX
derivatives have been developed via the functional-
ization of its phenyl ring.3 Other approaches involving the
replacement of a carboxyl unit by other donor groups
have also been developed.4 However, the majority of IBX
derivatives are aimed at improving their solubility in
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10.1021/ol202777h
Published on Web 11/14/2011
2011 American Chemical Society