Enhanced Reactivity of [Hydroxy(tosyloxy)iodo]benzene in Fluoroalcohol Media. Efficient Direct Synthesis of Thienyl(aryl)iodonium Salts.docVIP

Molecules 2010, 15, 1918-1931; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Enhanced Reactivity of [Hydroxy(tosyloxy)iodo]benzene in Fluoroalcohol Media. Efficient Direct Synthesis of Thienyl(aryl)iodonium Salts Motoki Ito 1, Chieko Ogawa 1, Nobutaka Yamaoka 2, Hiromichi Fujioka 1, Toshifumi Dohi 1,2 and Yasuyuki Kita 2,* 1 Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamada-oka, Suita, Osaka, Japan 2 College of Pharmaceutical Sciences, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga, Japan * Author to whom correspondence should be addressed; E-Mail: kita@ph.ritsumei.ac.jp; Tel.: +81-77-561-5829; Fax: +81-77-561-5829. Received: 3 February 2010; in revised form: 15 March 2010 / Accepted: 16 March 2010 / Published: 17 March 2010 Abstract: In this manuscript, we report clear evidence for the generation of aromatic cation radicals produced by using [hydroxy(tosyloxy)iodo]benzene (HTIB) in fluoroalcohol solvents such as 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoro- 2-propanol (HFIP). The single-electron-transfer (SET) oxidation ability of HTIB to give cation radicals was first established by ESR and UV measurements. The reaction was broadly applied to various thiophenes, and unique thienyliodonium salts were directly synthesized by this method in excellent yields without the production of any harmful byproducts. Keywords: [hydroxyl(tosyloxy)iodo]benzene; fluoroalcohol solvents; diaryliodonium salts; thiophenes; single-electron-transfer 1. Introduction In the last quarter of a century, the chemistry of hypervalent iodine has been extensively studied due to the increasing importance of greener synthetic processes [1–9]. A number of iodine(III) and iodine(V) reagents, e.g., phenyliodine(III) diacetate (PIDA), phenyliodine(III) bis(trifluoroacetate)  Molecules 2010, 15