RuCl₃-Catalyzed Oxidation of Iodoarenes with Peracetic Acid:  New Facile Preparation of Iodylarenes

Abstract

New facile methodology for the preparation of pentavalent iodine compounds using peracetic acid as an oxidant in the presence of catalytic amounts of ruthenium trichloride is described. The new procedure allows the preparation of several previously unknown iodylarenes bearing strongly electron-withdrawing CF3 groups in the aromatic ring.

Preparation and X-ray structure of 2-iodoxybenzenesulfonic acid (IBS) – a powerful hypervalent iodine(V) oxidant

“…2 ) the I–O bonds are much longer (≈2.5–2.6 Å). It is known from the literature that the preparation of iodine(V) species from ArI and an oxidant involves initial formation of ArIO followed by disproportionation to ArI and ArIO 2 [ 23 ]. Such disproportionation is significantly impeded or even impossible in the cyclic structure of 2-iodosylbenzenesulfonic acid.…”

Transition metal-mediated oxidations utilizing monomeric iodosyl- and iodylarene species

“…13 Further studies have demonstrated that the use of Oxone Ò as the oxidant instead of peracetic acid leads to even milder reaction conditions. In a typical procedure, treatment of iodobenzene with Oxone Ò in aqueous acetonitrile at room temperature in the presence of RuCl 3 (0.16 mol %) results in the formation of iodylbenzene (PhIO 2 ) n , which can be isolated from the reaction mixture in a 59% preparative yield (Scheme 2).…”

“…23 g, 5.0 mmol) according to the general procedure afforded 0.50 g (36%) of product, isolated as microcrystalline solid, mp 173e175 C. 1 H NMR (DMSO-d 6 ): d 7.94 (d,J¼7.5 Hz,1H),7.57 (m,3H), 3.22 (septet, 6.5 Hz, 1H), 1.29 (d, 7.0 Hz, 6H). 13 C NMR (DMSO-d 6 ): d 148. 7, 147.0, 132.1, 127.1, 126.9, 122.6, 33.0, 23.7 To a mixture of iodobenzene (0.204 g, 1 mmol) and Oxone Ò (0.33 g, 0.54 mmol) in 3 mL of aqueous acetonitrile (MeCN/H 2 O, 1:1) an aqueous solution of RuCl 3 (10 mL of standard 0.16 M solution; 0.…”

Estudo por espectrometria de massas de soluções de hidróxi(tosilóxi)iodobenzeno: propostas para mecanismos de desproporção

“…O mesmo grupo utilizou estratégia análoga em outras aplicações, 21 incluindo a preparação e aplicação de iodilarenos. [22][23][24] A desproporção de compostos de I(III) também foi investigada por Kita e colaboradores que, após realizarem a oxidação de alcoóis utilizando PhIO/KBr em água, 25 fizeram um estudo sobre o mecanismo da reação para averiguar o envolvimento de espécies de I(V), o que não se confirmou. 26 Apesar da importância da desproporção de reagentes de I(III), pouco se tem feito para entender o mecanismo desta reação.…”