115298-63-0Relevant academic research and scientific papers
New synthesis of diaryliodonium sulfonates from arylboronic acids
Carroll, Michael A.,Pike, Victor W.,Widdowson, David A.
, p. 5393 - 5396 (2000)
Diaryliodonium salts, precursors to [18F]fluoroaromatics, have been prepared, in a regioselective manner, from readily available arylboronic acids eliminating the need for acid sensitive and toxic organotin intermediates. (C) 2000 Elsevier Science Ltd.
Improved preparation of diaryliodonium triflates
Kitamura,Matsuyuki,Taniguchi
, p. 147 - 148 (1994)
A reagent prepared from a 1:2 molar ratio of (diacetoxy)iodobenzene [PhI(OAc)2] and trifluoromethanesulfonic acid (TfOH) reacts with aromatic compounds to give diaryliodonium triflates in fairly good yields. The high reactivity and high para se
Transition Metal-Free N-Arylation of Amino Acid Esters with Diaryliodonium Salts
Kervefors, Gabriella,Kersting, Leonard,Olofsson, Berit
, p. 5790 - 5795 (2021/03/08)
A transition metal-free approach for the N-arylation of amino acid derivatives has been developed. Key to this method is the use of unsymmetric diaryliodonium salts with anisyl ligands, which proved important to obtain high chemoselectivity and yields. The scope includes the transfer of both electron deficient, electron rich and sterically hindered aryl groups with a variety of different functional groups. Furthermore, a cyclic diaryliodonium salt was successfully employed in the arylation. The N-arylated products were obtained with retained enantiomeric excess.
Diverse Reactions of Thiophenes, Selenophenes, and Tellurophenes with Strongly Oxidizing I(III) PhI(L)2 Reagents
Egalahewa, Sathsara,Albayer, Mohammad,Aprile, Antonino,Dutton, Jason L.
supporting information, p. 1282 - 1288 (2017/02/15)
We report the outcomes of the reactions of aromatic group 16 thiophene, selenophene, and tellurophene rings with the I(III) oxidants PhI(OAc)(OTf) and [PhI(Pyr)2][OTf]2 (Pyr = pyridine). In all reactions, oxidative processes take place, with generation of PhI as the reduction product. However, with the exception of tellurophene with PhI(OAc)(OTf), +4 oxidation state complexes are not observed, but rather a variety of other processes occur. In general, where a C-H unit is available on the 5-membered ring, an electrophilic aromatic substitution reaction of either ?IPh or pyridine onto the ring occurs. When all positions are blocked, reactions with PhI(OAc)(OTf) give acetic and triflic anhydride as the identifiable oxidative byproducts, while [PhI(Pyr)2][OTf]2 gives pyridine electrophilic aromatic substitution onto the peripheral rings. Qualitative mechanistic studies indicate that the presence of the oxidizable heteroatom is required for pyridine to act as an electrophile in a substantial manner.
One-Pot C?H Functionalization of Arenes by Diaryliodonium Salts
Reitti, Marcus,Villo, Piret,Olofsson, Berit
supporting information, p. 8928 - 8932 (2016/07/26)
A transition-metal-free, mild, and highly regioselective synthesis of nitroarenes from arenes has been developed. The products are obtained in a sequential one-pot reaction by nitration of iodine(III) reagents with two carbon ligands, which are formed in situ from iodine(I). This novel concept has been extended to formation of aryl azides, and constitutes an important step towards catalytic reactions with these hypervalent iodine reagents. An efficient nitration of isolated diaryliodonium salts has also been developed, and the mechanism is proposed to proceed by a [2,2] ligand coupling pathway.
Metal-free n -arylation of secondary amides at room temperature
Tinnis, Fredrik,Stridfeldt, Elin,Lundberg, Helena,Adolfsson, Hans,Olofsson, Berit
, p. 2688 - 2691 (2015/06/16)
The arylation of secondary acyclic amides has been achieved with diaryliodonium salts under mild and metal-free conditions. The methodology has a wide scope, allows synthesis of tertiary amides with highly congested aryl moieties, and avoids the regioselectivity problems observed in reactions with (diacetoxyiodo)benzene.
Arylation with unsymmetrical diaryliodonium salts: A chemoselectivity study
Malmgren, Joel,Santoro, Stefano,Jalalian, Nazli,Himo, Fahmi,Olofsson, Berit
, p. 10334 - 10342 (2013/09/02)
Phenols, anilines, and malonates have been arylated under metal-free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new "anti-ortho effect" has been identified in the arylation of malonates. Several "dummy groups" have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal-free reagents. Copyright
Metal-free arylation of oxygen nucleophiles with diaryliodonium salts
Jalalian, Nazli,Petersen, Tue B.,Olofsson, Berit
, p. 14140 - 14149,10 (2012/12/12)
Phenols and carboxylic acids are efficiently arylated with diaryliodonium salts. The reaction conditions are mild, metal free, and avoid the use of halogenated solvents, additives, and excess reagents. The products are obtained in good-to-excellent yields after short reaction times. Steric hindrance is very well tolerated, both in the nucleophile and diaryliodonium salt. The scope includes ortho- and halo-substituted products, which are difficult to obtain by metal-catalyzed protocols. Many functional groups are tolerated, including carbonyl groups, heteroatoms, and alkenes. Unsymmetric salts can be chemoselectively utilized to obtain products with hitherto unreported levels of steric congestion. The arylation has been extended to sulfonic acids, which can be converted to sulfonate esters by two different approaches. With recent advances in efficient synthetic procedures for diaryliodonium salts the reagents are now inexpensive and readily available. The iodoarene byproduct formed from the iodonium reagent can be recovered quantitatively and used to regenerate the diaryliodonium salt, which improves the atom economy. Copyright
Fluoride-promoted ligand exchange in diaryliodonium salts
Wang, Bijia,Cerny, Ronald L.,Uppaluri, Shriharsha,Kempinger, Jayson J.,Dimagno, Stephen G.
body text, p. 1113 - 1121 (2011/02/25)
Diaryliodonium salts are shown to undergo rapid, fluoride-promoted aryl exchange reactions at room temperature in acetonitrile. Aryl exchange is shown to be exquisitely sensitive to the concentration of fluoride ion in solution; fast exchange is observed as the fluoride concentration approaches a stoichiometric amount at 50 mM substrate concentration. The reaction is slowed, but not halted if benzene is the solvent, indicating that free fluoride ion or a four-coordinate anionic I(III) species may be responsible for the exchange. The fluoride-promoted aryl exchange reaction is general and allows direct measurement of the relative stabilities of diaryliodonium salts featuring different aryl substituents. The aryl exchange reaction may be of practical use for the preparation of hitherto inaccessible diaryliodonium salts, thus it also has implications for labeling radiotracers for molecular imaging with 18F-fluoride (t1/2 = 109.7 min).
One-pot synthesis of diaryliodonium salts using toluenesulfonic acid: A fast entry to electron-rich diaryliodonium tosylates and triflates
Zhu, Mingzhao,Jalalian, Nazli,Olofsson, Berit
, p. 592 - 596 (2008/12/22)
A direct synthesis of symmetric and unsymmetric electron-rich diaryliodonium salts is described. The use of MCPBA and toluenesulfonic acid delivers diaryliodonium tosylates in high yields. An in situ anion exchange has also been developed, giving access to the corresponding triflate salts. Georg Thieme Verlag Stuttgart.
