Synthesis 2012; 44(8): 1183-1189
DOI: 10.1055/s-0031-1290579
special topic
© Georg Thieme Verlag Stuttgart · New York

μ-Oxo-Bridged Hypervalent Iodine(III) Compound as an Extreme Oxidant for Aqueous Oxidations

Toshifumi Dohi
a  College of Pharmaceutical Sciences, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga, 525-8577, Japan, Fax: +81(77)5615829   Email: kita@ph.ritsumei.ac.jp
,
Tomofumi Nakae
a  College of Pharmaceutical Sciences, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga, 525-8577, Japan, Fax: +81(77)5615829   Email: kita@ph.ritsumei.ac.jp
,
Naoko Takenaga
b  Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamada-oka, Suita, Osaka, 565-0871, Japan
,
Teruyoshi Uchiyama
a  College of Pharmaceutical Sciences, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga, 525-8577, Japan, Fax: +81(77)5615829   Email: kita@ph.ritsumei.ac.jp
,
Kei-ichiro Fukushima
a  College of Pharmaceutical Sciences, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga, 525-8577, Japan, Fax: +81(77)5615829   Email: kita@ph.ritsumei.ac.jp
,
Hiromichi Fujioka
b  Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamada-oka, Suita, Osaka, 565-0871, Japan
,
Yasuyuki Kita*
a  College of Pharmaceutical Sciences, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga, 525-8577, Japan, Fax: +81(77)5615829   Email: kita@ph.ritsumei.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 14 February 2012

Accepted: 20 February 2012

Publication Date:
16 March 2012 (online)

Abstract

We have found that in aqueous oxidations the μ-oxo-bridged hypervalent iodine trifluoroacetate reagent 1 {[(PhI(OCOCF3)]2O} is generally more reactive than the corresponding monomeric reagent, especially toward phenolic substrates. μ-Oxo-bridged 1 in aqueous media thus provided dearomatized quinones 3 in excellent yields in most cases compared to conventional phenyliodine(III) diacetate and bis(trifluoroacetate), as a result of the rapid oxidation of both phenols and naphthols 2. Furthermore, the oxidation reactions proceeded even in water using water-soluble μ-oxo oxidant 1, which has promise for μ-oxo-bridged reagent 1 to become the favored reagent over hydrophobic phenyliodine(III) diacetate and bis(trifluoroacetate).

 
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