- Characterization of species present in aqueous solutions of [hydroxy(mesyloxy)iodo]benzene and [hydroxy(tosyloxy)iodo]benzene
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Upon solution in water, both [hydroxy(mesyloxy)iodo]benzene and [hydroxy(tosyloxy)iodo]benzene undergo complete ionization to give the hydroxy(phenyl)iodonium ion (PhI+OH) and the corresponding sulfonate ion (RSO2O-) as fully solvated species, i.e., 'free' ions. The phenyliodonium solution species do not form ion pairs with the organosulfonate ions. The hydroxy(phenyl)iodonium ion is presumed to be ligated with at least one water molecule at an apical site of the iodine(m) atom originally occupied by the sulfonate ion. In view of the relative basicities of HO- and H2O, the hydroxy ligand of the [hydroxy(aquo)iodo]benzene ion (PhI+(OH2)OH) is expected to be strongly bound and the water ligand is expected to be weakly bound to the iodine(m) center. This species has a pK(A) at (4.30 ± 0.05). PhI+(OH2)OH and its conjugate base are present in equilibrium with the [hydroxy(auqo)]-μ-oxodiphenyldiiodine cation (Ph(HO)I-O-I+(OH2)Ph). This μ-oxo dimer is present at significant levels even in relatively dilute solutions as the combination equilibrium constant is (540 ± 50). This dimer can be protonated, and the pK(A) of the conjugate acid is ~2.5. The equilibrium constant for dimerization of [oxo(aquo)iodo]benzene (PhI+(OH2)O-), the most important monomer in acidic solutions, is ~8.6.
- Richter, Helen Wilkinson,Cherry, Brian R.,Zook, Teresa D.,Koser, Gerald F.
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- Facile one-pot preparation of [hydroxy(sulfonyloxy)iodo]arenes from iodoarenes with MCPBA in the presence of sulfonic acids
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Various [hydroxy(sulfonyloxy)iodo]arenes were simply and efficiently obtained in high yields from the reaction of iodoarenes and MCPBA in the presence of sulfonic acids in a small amount of chloroform at room temperature, through a one-pot procedure. Georg Thieme Verlag Stuttgart.
- Yamamoto, Yukiharu,Togo, Hideo
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- Rapid microwave-promoted solvent-free synthesis of hypervalent iodine reagents
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Hypervalent hydroxy(sulfonyloxy)iodoarenes, hydroxy(phosphoryloxy) iodoarenes and bis(trifluoroactoxy)iodobenzene have been synthesised by a fast and convenient solvent-free ligand exchange reaction from the (diacetoxyiodo)arene under microwave irradiation, providing a simple method for the synthesis of these hypervalent iodine reagents in good yield and in a short time.
- Zhou, Zhongshi,He, Xuehan
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- α-Sulfonyloxylation of 1,3-dicarbonyl compounds utilizing hypervalent iodine(iii) reagent: Construction of quaternary carbon center
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An efficient method for direct α-sulfonyloxylation of various sterically hindered 1,3-dicarbonyl compounds has been developed under mild reaction conditions. The yields of desired products is up to 90% and a plausible mechanism was accordingly proposed.
- Liu, Ruojuan,Wang, Junzheng,Hu, Wen,Zhang, Xiaohui,Xiong, Yan
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- Facile synthesis of Koser's reagent and derivatives from iodine or aryl iodides
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The first one-pot synthesis of neutral and electron-rich [hydroxy(tosyloxy)iodo]arenes (HTIBs) from iodine and arenes is presented, thereby avoiding the need for expensive iodine(III) precursors. A large set of HTIBs, including a polyfluorinated analogue, can be obtained from the corresponding aryl iodide under the same conditions. The reaction proceeds under mild conditions, without excess reagents, and is fast and high-yielding. Together, the two presented routes give access to a wide range of HTIBs, which are useful reagents in a variety of synthetic transformations.
- Merritt, Eleanor A.,Carneiro, Vania M. T.,Silva Jr., Luiz F.,Olofsson, Berit
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experimental part
p. 7416 - 7419
(2011/02/22)
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- Solvent-free reactions with hypervalent iodine reagents
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(Chemical Equation Presented) We describe solvent-free reactions for the synthesis of hypervalent iodine reagents and their use in solid-state reactions. Improved yields and higher purities of the products are observed.
- Yusubov, Mekhman S.,Wirth, Thomas
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p. 519 - 521
(2007/10/03)
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- NOVEL REAGENTS CONTAINING HYPERVALENT IODINE AND THEIR USE FOR ELECTROPHILIC ADDITIONS TO OLEFINS
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A series of novel I(III) containing reagents have been developed and their electrophilic reactions with olefins giving vic-disubstituted derivatives (including vic-ditriflates) are described.
- Zefirov, Nikolai S.,Zhdankin, Viktor V.,Dan'kov, Yu. V.,Caple, Ronald,Berglund, Bruce A.
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p. 3971 - 3974
(2007/10/02)
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