- One-Pot C?H Functionalization of Arenes by Diaryliodonium Salts
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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.
- Reitti, Marcus,Villo, Piret,Olofsson, Berit
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p. 8928 - 8932
(2016/07/26)
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- Metal-free n -arylation of secondary amides at room temperature
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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.
- Tinnis, Fredrik,Stridfeldt, Elin,Lundberg, Helena,Adolfsson, Hans,Olofsson, Berit
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p. 2688 - 2691
(2015/06/16)
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- Metal-Free C-Arylation of Nitro Compounds with Diaryliodonium Salts
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An efficient, mild, and metal-free arylation of nitroalkanes with diaryliodonium salts has been developed, giving easy access to tertiary nitro compounds. The reaction proceeds in high yields without the need for excess reagents and can be extended to α-arylation of nitroesters. Nitroalkanes were selectively C-arylated in the presence of other easily arylated functional groups, such as phenols and aliphatic alcohols.
- Dey, Chandan,Lindstedt, Erik,Olofsson, Berit
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p. 4554 - 4557
(2015/09/28)
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- Metal-free one-pot synthesis of benzofurans
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Ethyl acetohydroxamate was efficiently arylated with diaryliodonium salts at room temperature under transition-metal-free conditions. The obtained O-arylated products were reacted in situ with ketones under acidic conditions to yield substituted benzo[b]furans through oxime formation, [3,3]-rearrangement, and cyclization in a fast and operationally simple one-pot fashion without using excess reagents. Alternatively, the O-arylated products could be isolated or transformed in situ to aryloxyamines or O-arylaldoximes. The methodology was applied to the synthesis of Stemofuran A and the formal syntheses of Coumestan, Eupomatenoid 6, and (+)-machaeriol B. Just add salt! A metal-free, room temperature arylation of ethyl acetohydroxamate, followed by an in situ reaction with ketones under acidic conditions yielded substituted benzo[b]furans in a fast and operationally simple one-pot fashion without using excess reagents (see scheme). Alternatively, the O-arylated products could be isolated, hydrolyzed in situ to aryloxyamines, or transformed to O-arylaldoximes. The efficiency of the methodology was demonstrated by the formal synthesis of several biologically active benzofurans.
- Ghosh, Raju,Stridfeldt, Elin,Olofsson, Berit
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p. 8888 - 8892
(2014/07/22)
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- Facile preparation of unsymmetrical diaryl ethers from unsymmetrical diaryliodonium tosylates and phenols with high regioselectivity
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Unsymmetrical diaryl ethers were efficiently obtained in good yields by the reactions of aryl(4-methoxyphenyl)iodonium tosylates with phenols, and aryl(2,4-dimethoxyphenyl)iodonium tosylates with phenols, in the presence of potassium carbonate in acetonitrile, respectively. The latter iodonium tosylates provided the corresponding unsymmetrical diaryl ethers in good yields with high regioselectivities, together with the quantitative formation of 1-iodo-2,4-dimethoxybenzene. Georg Thieme Verlag Stuttgart New York.
- Kakinuma, Yohji,Moriyama, Katsuhiko,Togo, Hideo
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p. 183 - 188
(2013/02/23)
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- Halogen exchange via a halogenation of diaryliodonium salts with cuprous halide
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An efficient halogenation reaction has been developed with diaryliodonium salts and cuprous halides. Various diaryliodonium salts 1 could perform the reaction with readily available CuBr or CuCl in CH3CN at 80°C, assembling bromoarenes or chloroarenes in up to 92% yields. This provides us a method for the transformation from iodoarenes to other haloarenes.
- Li, Jian,Liu, Li,Ding, Dong,Sun, Jiang-Tao
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p. 541 - 548
(2014/01/06)
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- Metal-free synthesis of aryl esters from carboxylic acids and diaryliodonium salts
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An efficient arylation of carboxylic acids with diaryliodonium salts has been developed, giving aryl esters in high yields within short reaction times for both aromatic and aliphatic substrates. The transition-metal-free conditions are compatible with a range of functional groups, and good chemoselectivity is observed with unsymmetric diaryliodonium salts. Furthermore, steric hindrance in the ortho positions is well tolerated both in the carboxylic acid and in the diaryliodonium salt, yielding aryl esters that cannot be obtained via other esterification protocols.
- Petersen, Tue B.,Khan, Rehan,Olofsson, Berit
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p. 3462 - 3465
(2011/08/07)
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- One-pot synthesis of diaryliodonium salts using toluenesulfonic acid: A fast entry to electron-rich diaryliodonium tosylates and triflates
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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.
- Zhu, Mingzhao,Jalalian, Nazli,Olofsson, Berit
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p. 592 - 596
(2008/12/22)
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- Versatile direct dehydrative approach for diaryliodonium(III) salts in fluoroalcohol media
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We have found that the use of fluoroalcohol media greatly enhanced the efficiency and scope of the direct dehydrative condensation of arenes 1 and hypervalent iodine(iii) compounds; the present clean method has a broad range of applicability as well as un
- Dohi, Toshifumi,Ito, Motoki,Morimoto, Koji,Minamitsuji, Yutaka,Takenaga, Naoko,Kita, Yasuyuki
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p. 4152 - 4154
(2008/03/27)
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- Sulfonates, polymers, resist compositions and patterning process
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A sulfonate compound having formula (1) is novel wherein R1 to R3 are H, F or C1-20 alkyl or fluoroalkyl, at least one of R1 to R3 contains F. A polymer comprising units derived from the sulfonate compound is used as a base resin to formulate a resist composition which is sensitive to high-energy radiation, maintains high transparency at a wavelength of up to 200 nm, and has improved alkali dissolution contrast and plasma etching resistance
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- Novel tertiary (meth)acrylates having lactone structure, polymers, resist compositions and patterning process
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Novel tertiary (meth)acrylate compounds having a lactone structure are polymerizable into polymers having improved transparency, especially at the exposure wavelength of an excimer laser and dry etching resistance. Resist compositions comprising the polymers are sensitive to high-energy radiation, have a high resolution, and lend themselves to micropatterning with electron beams or deep-UV rays.
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- Process for producing onium salt derivative and novel onium salt derivative
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The invention provides a high-yield method for producing onium salt derivatives useful as agents, such as acid-generators, employed in chemically amplified resists; and to provide novel onium salt derivatives. Reaction of an onium salt derivative containi
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- Novel anthracene derivative and radiation-sensitive resin composition
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A novel anthracene derivative useful as an additive to a radiation-sensitive resin composition is disclosed. The anthracene derivative has the following formula (1), wherein R1 groups individually represent a hydroxyl group or a monovalent organic group having 1-20 carbon atoms, n is an integer of 0-9, X is a single bond or a divalent organic group having 1-12 carbon atoms, and R2 represents a monovalent acid-dissociable group. The radiation-sensitive resin composition comprises the anthracene derivative of the formula (1), a resin insoluble or scarcely soluble in alkali, but becomes alkali soluble in the presence of an acid, and a photoacid generator. The composition is useful as a chemically-amplified resist for microfabrication utilizing deep ultraviolet rays, typified by a KrF excimer laser and ArF excimer laser.
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- Novel carbazole derivative and chemically amplified radiation-sensitive resin composition
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A carbazole derivative of the following formula (1), wherein R1 and R2 individually represent a hydrogen atom or a monovalent organic group, or R1 and R2 form, together with the carbon atom to which R1 and R2 bond, a divalent organic group having a 3-8 member carbocyclic structure or a 3-8 member heterocyclic structure, and R3 represents a hydrogen atom or a monovalent organic group. The carbazole derivative is suitable as an additive for increasing sensitivity of a chemically amplified resist. A chemically amplified radiation-sensitive resin composition, useful as a chemically amplified resist, comprising the carbazole derivative is also disclosed.
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- Facile synthesis of substituted diaryliodonium tosylates by treatment of aryltributylstannanes with Koser's reagent
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A facile synthesis of substituted diaryliodonium tosylates (toluene-p-sulfonates) was developed, based on the treatment of substituted aryltributylstannanes with Koser's reagent [hydroxy(tosyloxy)iodobenzene]. In this manner, several new diaryliodonium sa
- Pike, Victor W.,Butt, Faisal,Shah, Aneela,Widdowson, David A.
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p. 245 - 248
(2007/10/03)
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- Oxidative Anion Metatheses in Diaryliodonium Iodides and Chlorides
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Oxidative anion metatheses in the crude title iodides and chlorides produced the corresponding pure hydrogensulfates, nitrates, tetrafluoroborates, triflates, tosylates, as well as bromides and chlorides (only from the iodides) in 54-86% yields. These procedures are easier and shorter than earlier methods. By using modified oxidative metatheses in the title iodides (in the presence of HBr or HCl) it was possible either to isolate, or to detect only, the intermediate dihaloiodates(I). [Ar2I]+[IX2]- (X = Br or Cl). A complex Ph2I+Cl- -1/2I2 was also obtained in 56% yield. Tetraethylammonium iodide was similarly converted into pure tetrafluoroborate or dibromoiodate(I) in 75 and 76% yields, respectively.
- Kazmierczak, Pawel,Skulski, Lech
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p. 219 - 224
(2007/10/03)
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- A short-cut synthesis of diaryliodonium bromides followed by oxidative anion metatheses
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This paper reports a one-pot synthesis of the title bromides (in 20-88% crude yields) from iodoarenes oxidized with the CrO3/AcOH/Ac2O/H2SO4 liquid mixture, then coupled in situ with arenes and, finally, precipitated out with a KBr solution. Similarly, diaryliodonium perchlorates and iodides are obtained in 40-89% crude yields. Oxidative anion metatheses in the crude title bromides produce the respective pure diaryliodonium tetrafluoroborates, tosylates, trifluoroacetates, hydrosulfates, nitrates, and chlorides in 57-80% yields. These new preparative procedures are easier and shorter than many earlier methods.
- Kazmierczak,Skulski
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p. 1027 - 1032
(2007/10/02)
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- New Methodology in Iodonium Salt Synthesis. Reactions of arenes with Aryltrimethylsilanes
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arenes react with aryltrimethylsilanes in acetonitrile to give diaryliodonium tosylates.The phenyliodinations proceed with silicon-carbon bond cleavage, thus allowing control of substituent placement in both rings.With bis(trimethyl
- Koser, Gerald F.,Wettach, Richard H.,Smith, Carol S.
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p. 1543 - 1544
(2007/10/02)
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