Iodonium salts syntheses with

The O-arylation of appropriate phenols using symmetrical iodonium salts has been employed in the synthesis of hydroxylated and methoxylated polybrominated diphenyl ethers, some of which are related to natural products [872,873]. For example, several polybrominated diphenyl ethers 680 have been prepared by the reaction of iodonium salt 678 with phenols 679 in iV,iV-dimethylacetamide (DMAC) solution in the presence of base (Scheme 3.272) [872]. 

Oxo-bridged diiodonium triflate [Zefirov s reagent), a useful reagent for the synthesis of triflate esters and iodonium salts, can be prepared by the treatment of lodosobenzene with triflic anhydride [92] or by the reaction of lodobenzene diacetate with tnflic acid [93] (equation 44). 

Two approaches have been applied for the synthesis of imidazo[2,l + thia/,ole ring systems. Reaction of 2-mercapto-benzimidazole with perfluoro-2-methylpent-2-ene in the presence of triethylamine gave compound 419 (Equation 192), and cyclocondensation of 2-imidazolidinethione with the alkynyl(phenyl)iodonium salt 420 afforded product 421 (Equation 193) <2001RCB1446, 2003JCM715>. 

The unique reactivity pattern of alkynyl iodonium salts discussed in Sections II,A.2 and II,D,la can also serve as two-carbon conjunctive reagents in the synthesis of pyrroles, dihydropyrroles, and indoles. Feldman et al. found that combination of alkyl or aralkyl tosylamide anions 101 with phenyl(propynyl)iodonium triflate (102) furnishes the corresponding dihydropyrroles 103 (95JOC7722) (Scheme 28). 

Silyl ethers of aliphatic alcohols are inert towards strong bases, oxidants (ozone [81], Dess-Martin periodinane [605], iodonium salts [610,611], sulfur trioxide-pyridine complex [398]), and weak acids (e.g., 1 mol/L HC02H in DCM [605]), but can be selectively cleaved by treatment with HF in pyridine or with TBAF (Table 3.32). Phenols can also be linked to insoluble supports as silyl ethers, but these are less stable than alkyl silyl ethers and can even be cleaved by treatment with acyl halides under basic reaction conditions [595], Silyl ether attachment has been successfully used for the solid-phase synthesis of oligosaccharides [600,601,612,613] and peptides [614]. 

Iodobenzene [591-50-4], C6HBI, mol wt 204.02, 62.23% I, mp —30°C, bp 188—189°C, is a colodess liquid that rapidly becomes yellow and has a characteristic odor. It is insoluble in water, but completely miscible with alcohol, chloroform, and ether. It has a density of 1.832 g/mL at 20°C and a refractive index of 1.621 at 4°C. Iodobenzene is prepared by the reaction of iodine and benzene in the presence of an oxidizing agent and from benzeneiazonium sulfate and potassium iodide (122). Iodobenzene is used as a heavy liquid for refractive index determinations, but probably its principal use is in the synthesis of iodoso compounds, RIO iodoxy compounds, RI02 and iodonium salts, R IX. 

A special method was needed for the synthesis of bis(pentafluorophenyl)-iodonium salts this was achieved either by reaction of pentafluoroiodobenzene with C6F5Xe+ TfO- or, more conveniently, from pentafluorobenzene and I(OOC-CF3)3 in strongly acidic conditions [101]. 

Special iodonium salts. A range of o-trimethylsilyl-phenyliodonioarenes [111] and heteroarenes [112] as well as some similar Wc-compounds coming from norbornadiene [113] and o-carborane [114] have been obtained from the corresponding bis trimethylsilyl precursors upon reaction with one equivalent of (diacetoxyiodo)benzene. These compounds are useful for their facile in situ conversion into benzyne-type intermediates for benzyne itself the whole procedure is available in Organic Syntheses [115]. A recent improvement involved the synthesis of a new benzyne precursor illustrated in Scheme 38 [116]. 

In some instances the iodonium salt is not isolated but may react in situ with nucleophiles, for example upon hydrozirconation of alkynyl(phenyl)iodonium salts with Cp2Zr(H)Cl (Scheme 42) these salts were used for the stereoselective synthesis of some halogenated alkenes [128]. 

The use of hypervalent iodine reagents in carbon-carbon bond forming reactions is summarized with particular emphasis on applications in organic synthesis. The most important recent methods involve the radical decarboxylative alkylation of organic substrates with [bis(acyloxy)iodo]arenes, spirocyclization of para- and ortho-substituted phenols, the intramolecular oxidative coupling of phenol ethers, and the reactions of iodonium salts and ylides. A significant recent research activity is centered in the area of the transition metal-mediated coupling reactions of the alkenyl-, aryl-, and alkynyliodonium salts. 

A similar procedure was used for the preparation of several bicyclic enediynes 78 from bis-iodonium salts 62 and alkynylstannanes (Scheme 36) [61]. This coupling reaction was recently utilized in the synthesis of novel dinu-clear complexes with a photochromic bridge [62]. 

Alkynyl(phenyl)iodonium salts can be used for the preparation of substituted alkynes by the reaction with carbon nucleophiles. The parent ethynyliodonium tetrafluoroborate 124 reacts with various enolates of /J-dicarbonyl compounds 123 to give the respective alkynylated products 125 in a high yield (Scheme 51) [109]. The anion of nitrocyclohexane can also be ethynylated under these conditions. A similar alkynylation of 2-methyl-1,3-cyclopentanedione by ethynyliodonium salt 124 was applied in the key step of the synthesis of chiral methylene lactones [110]. 

The formation of carbon-heteroatom bonds can be effected by reactions of hypervalent iodine reagents with a wide range of organic substrates and inorganic nucleophiles, and represents one of the most popular applications of organoiodine(III) compounds [1-10]. Except for C-I(III) bond forming reactions used for the synthesis of iodanes and iodonium salts, C-heteroatom bond formation is almost always accompanied by reduction of the hypervalent iodine reagents to iodine(I) compounds. 

In a rare example of the use of iodonium salts for heteroatom-heteroatom bond formation, diaryliodonium halides were employed with sodium 0,0-diethyl phosphoroselenolate for a one-pot synthesis of diaryl diselenides (Scheme 9) [27]. These transformations probably occur via arylation of the phosphoroselenolate salt with the diaryliodonium ions, hydrolysis of the resulting aryl phosphoroselenolates with sodium hydroxide, and air oxidation of the arene-selenide ions thus produced. 

Enynes were prepared in good yield from alkynyl iodonium salts and alkenylcopper reagents, stereospecifically. This approach was suitable for the synthesis of conjugated enynes, using a trisubstituted alkene with complete retention of its geometry [47], 1,3-Diynes were similarly obtained by coupling alkynyl iodonium... 

Finally, vinyl(tri-rc-butyl)stannanes have also been utilized with iodosylbenzene and Meerwein s reagent126 for the synthesis of the ( rr-butylcyclohexenyl)iodonium tetrafluoroborate shown in equation 162 and with iodosylbenzene/BF3-etherate to give the (ketovinyl)iodonium salt shown in equation 169128. 

Attempts to prepare a (/ -fiuorovinyl)iodonium salt from l-decynyl(phenyl)iodonium tetrafluoroborate by the procedures employed for / -chloro- and (/ -bromovinyl)iodonium halides have been unsuccessful103. Admixture of the decynyliodonium salt and lithium fluoride in acetic acid ultimately (2 days, rt) leads to l-acetoxy-2-decanone103. (Z )-(/ -Fluoro-jS-perfluoroalkylvinyl)iodonium triflates, on the other hand, can be made by the treatment of (1H, li/-perfluoroalkyl)phenyliodonium triflates with sodium hydride (equation 178)136. Apart from 2-fluoro-l-hexadecenyl(phenyl)iodonium chloride (synthesis not described)104, these are the only reported examples of (/ -fluorovinyl)iodonium salts. 

Two examples of Pd(II)-catalyzed carbomethoxylations of vinyl(phenyl)iodonium salts have been reported (equations 251 and 252)125,126. The mild reaction conditions and stereospecificity of carbonylation recommend further applications of vinyliodonium compounds for the synthesis of a,/ -unsaturated carboxylate esters. By way of comparison, similar carbobutoxylations of vinyl halides (Br, I) typically require higher temperatures (60-100 °C) and longer reaction times, and they sometimes proceed with low stereospecificity151. 

This synthesis of 1,2,3,4-tetraphenylnaphthalene (7) demonstrates the transient existence of benzyne (5), a hydrocarbon that has not been isolated as such. The precursor, diphenyliodonium-2-carboxylate (4), is heated in an inert solvent to a temperature at which it decomposes to benzyne, iodobenzene, and carbon dioxide in the presence of tetraphenylcyclo-pentadienone (6) as trapping agent. The preparation of the precursor (4) illustrates oxidation of a derivative of iodobenzene to an iodonium salt (2) and the Friedel-Crafts-like reaction of the substance with benzene to form the diphenyliodonium salt (3). Neutralization with ammoniuim hydroxide then liberates the precursor, inner salt (4), which, when obtained by crystallization from water, is the monohydrate. 

Pirguliyev, N. S., Brel, V. K., Zefirov, N. S., Stang, P. J. Stereoselective synthesis of conjugated alkenynes via palladium-catalyzed coupling of alkenyl iodonium salts with terminal alkynes. Tetrahedron 1999, 55, 12377-12386. 

Alkenylzirconium reagents Hydrozirconation of alkynes with Cp ZifHlCl followed by reaction with iodonium salts constitutes a method for synthesis of styrenes and enynes. In the latter case it can be seen that zirconium prefers attachment to the heterosubstituted carbon atom therefore, 1,1-difiinctionalized 1-alkenes are readily prepared, including those pairing Si/Se and Te/Te. ... 

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