Iodonium Triflate Research Articles

Iron(II)‐Catalyzed Direct Cyanation of Arenes with Aryl(cyano)iodonium Triflates

A direct oxidative cyanation of arenes under Fe(II) catalysis with 3,5-di(trifluoromethyl)phenyl(cyano)iodonium triflate (DFCT) as the cyanating agent has been developed. The reaction is applicable to wide range of aromatic substrates, including polycyclic structures and heteroaromatic compounds.

ChemInform Abstract: Copper(I)‐Catalyzed Cascade Dearomatization of 2‐Substituted Tryptophols with Arylidonium Salts.

AbstractFuro‐fused indolines bearing two quaternary carbon centers are formed by the title reaction using diaryl‐ or vinyl(phenyl)iodonium triflates and an optimized copper catalyst.

On the Reaction of 1,3-Diphenylisobenzofuran and (2-Iodoethynyl)(phenyl)iodonium Triflate. A Unique Case of Oxygen Transfer from the Diels-Alder Adduct to the Diene

Reaction of 1,3-diphenylisobenzofuran (DPIBF) with 2-(iodoethynyl)(phenyl)-iodonium triflate at room temperature gave the expected Diels-Alder adduct, but using an excess of DFIBF (2 equiv.) and performing the reaction at 55 °C or heating at this temperature during the concentration stage, the initial orange solution or product mixture became dark brown and the products 1,2-phenylene-1,2-bis(phenylmethanone) and 2-(3-iodo-1,4-diphenylnaphthyl)(phenyl)iodonium triflate were obtained, which suggests an oxygen transfer between DPIBF and the initial adduct.

Enantioselective α-vinylation of aldehydes via the synergistic combination of copper and amine catalysis.

The enantioselective α-vinylation of aldehydes using vinyl iodonium triflate salts has been accomplished via the synergistic combination of copper and chiral amine catalysis. These mild catalytic conditions provide a direct route for the enantioselective construction of enolizable α-formyl vinylic stereocenters without racemization or olefin transposition. These high-value coupling adducts are readily converted into a variety of useful olefin synthons.

ChemInform Abstract: Enantioselective α‐Arylation of N‐Acyloxazolidinones with Copper(II)‐Bisoxazoline Catalysts and Diaryliodonium Salts.

AbstractA variety of N‐acyloxazolidinones is applied to the reaction with the mesityl(phenyl)iodonium triflate to afford the α‐phenylated products with high yields and enantioselectivities.

Alkynylation of Benzotriazole with Silylethynyliodonium Triflates. Regioselective Synthesis of 2-Ethynyl-2H-benzotriazole Derivatives

Phenyl(trimethylsilylethynyl)iodonium and tert-butyldimethylsilylethynyl(phenyl)iodonium triflates were applied to alkynylation of benzotriazole. Treatment of the silylethynyliodonium triflates with the potassium salt of benzotriazole ion in (t)BuOH and CH(2)Cl(2) gave 2-(trimethylsilylethynyl)-2H-1,2,3-benzotriazole and 2-(tert-butyldimethylsilylethynyl)-2H-1,2,3-benzotriazole in 74% and 76% yields, respectively. The regioisomers, 1-silylethynyl-1H-1,2,3-benzotriazole derivatives, were minor. In both cases of the silyl-substitued ethynyliodonium salts, novel regioselective alkynylation of benzotriazole at the 2 position was observed.

ChemInform Abstract: (Dicyano)iodonium Triflate. Novel Iodonium Species and a Versatile Reagent for the Preparation of Iodonium Salts via an Iodonium Transfer Reaction with Organostannanes.

Abstract (Dicyano)iodonium triflate (NC)2I+−OTf can be prepared by the reaction of O=I-OTf with cyanotrimethylsilane and isolated as an air sensitive crystalline solid unstable at room temperature. This compound generated in situ reacts with tributyltin derivatives of various aromatic compounds or acetylenes at −40 °C forming the corresponding iodonium salts in good yield.

ChemInform Abstract: Alkynyliodonium Salts in Organic Synthesis. Preparation of Anellated Dihydropyrroles by Cascade Addition/Bicyclization of Dienyltosylamide Anions with Phenyl(propynyl)iodonium Triflate.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Primary Vinyl Cations in Solution: Kinetics and Products of β,β-Disubstituted Alkenyl(aryl)iodonium Triflate Fragmentations.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: A Potential Chemical Source of C2.

Thermolysis of ethynyl(phenyl)iodonium triflate, 1, in the presence of cyclooctatetraene generates naphthalene in a reaction involving free C2 or in which 1 acts as a C2 donor.

Preparation of Replicated Resin Mold for UV Nanoimprint Using Reworkable Dimethacrylate

Reworkable dimethacrylate which has adamantyl moiety and hemiacetal ester moiety in a molecule was synthesized. UV curing and photo-induced degradation of the UV cured resins were investigated. On UV irradiation at 365 nm, dimethacrylate containing 2,2-dimethoxy-2-phenylacetophenone and di(4-tert-butylphenyl)iodonium triflate became insoluble in methanol. The UV cured resin degraded under acidic conditions. Present resins were applied to UV nanoimprint lithography (UV-NIL) using 365 nm-light and fine line/space patterns on quartz plate were obtained. These patterns (primary patterns) were used as a mold for making a replicated resin mold. By using the primary patterns as a mold, multifunctional acrylates were UV imprinted on Si substrate. After acids were generated in the primary patterns by baking or UV exposure at 254 nm, the sample was dipped in methanol to remove the primary patterns and a replicated resin mold was obtained on Si substrate. UV-NIL using the replicated mold was successfully accomplished.

ChemInform Abstract: O‐Arylation of Carboxylic Acids Using (Phenyl)[2‐(trimethylsilyl)phenyl]iodonium Triflate as a Precursor of Arynes.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

O‐Arylation of Carboxylic Acids using (Phenyl)[2‐(trimethylsilyl)phenyl]iodonium Triflate as a Precursor of Arynes

Using (phenyl)[2‐(trimethylsilyl)phenyl]iodonium triflate as a precursor of arynes, Larock's method for O‐arylation of carboxylic acids and arynes was developed. A variety of acids including simple aliphatic carboxylic acids, aromatic carboxylic acids, allenoic acids, and p‐toluenesulfonic acid under mild reaction conditions could generate the aryl esters.

A Novel Synthesis of Spiro(imidazolidine-2,3′-benzo[b]thiophene) by One-Pot Reaction of Arynes, Aryl Isothiocyanates and N-Heterocyclic Carbenes

A novel synthesis of spiro(imidazolidine-2,3′-­benzo[b]thiophene) by one-pot reaction of aryl isothiocyanates, N-heterocyclic carbenes and arynes using (phenyl)[2-(trimethyl­silyl)phenyl]iodonium triflate as precursor is reported.

Facile One‐Pot Synthesis of 2‐Aryl‐Substituted Nitriles and 2‐Aryl‐3‐keto Nitriles via Benzyne Reaction.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Facile One‐Pot Synthesis of 2‐Aryl‐substituted Nitriles and 2‐Aryl‐3‐keto Nitriles via Benzyne Reaction

2‐Aryl‐substituted nitriles were prepared in good to excellent yields in a one‐pot reaction by the reaction of benzyne, generated using neutral conditions from (phenyl)[o‐(trimethylsilyl)‐phenyl]iodonium triflate, and 2‐lithionitriles. 3‐Keto nitriles substituted at the 2‐position were obtained in good yields when these reactions were trapped with acid chlorides. The mechanism of the benzyne reaction in terms of a N‐lithiobenzocyclobutanimine intermediate is discussed.

Reaction of iodoarenes with potassium peroxodisulfate/trifluoroacetic acid in the presence of aromatics. Direct preparation of diaryliodonium triflates from iodoarenes

Abstract Diaryliodonium triflates have been directly prepared by reaction of some iodoarenes with aromatic substrates in good yields by using K2S2O8/CF3COOH/CH2Cl2. Treatment of a variety of iodoarenes with iodobenzene under the same conditions resulted in ligand transfer, and (4-iodophenyl)(phenyl)iodonium triflate was obtained. This procedure avoids the use of high temperature and severe reaction conditions.

Efficient generation and trapping of acylbenzynes from hypervalent iodine compounds

[5-Acyl-2-(trimethylsilyl)phenyl]iodonium triflates were prepared for the generation of benzynes bearing ketone function. Treatment of the iodonium triflates with Bu 4NF in CH 2Cl 2 in the presence of furan at room temperature gave 6-acyl-1,4-epoxy-1,4-dihydronaphthalenes in high yields. The mild conditions and the tolerance of the ketone function on benzyne generation are attributable to the advantage of hypervalent iodine compounds.

Formation of New Alkynyl(phenyl)iodonium Salts and Their Use in the Synthesis of Phenylsulfonyl Indenes and Acetylenes

The preparation of phenylsulfonyl indene derivatives and phenylsulfonyl-acetylenes from readily available alkynyl(phenyl)iodonium tetrafluoroborates and triflates was investigated using phenylsulfinate as nucleophile.

Facile Synthesis of 2-Substituted 4H-1,3-Thiazines and 3-Substituted 1,2-Isothiazoles via Benzyne Intermediates

Substituted 2-dialkylamino-4H-1,3-benzothiazineswere Synthesizedby the reaction of (phenyl)[o-(trimethylsilyl)aryl]iodonium triflates and dialkyl-aminothiazadienes in the presence of 1.5 equivalent of Bu 4 NF. However, when these reactions were carried out in the presence of 4 equivalents of Bu 4 NF, 3-substituted 1,2-benzisothiazoles were obtained. Additionally, the reaction of phenyl[(3-trimethylsilyl)-2-naphthyl]iodonium triflate with dialkylaminothia-zadienes in the presence of Bu 4 NF gave 3-substituted 1,2-naphthisothiazoles. A possible mechaism for the latter reaction involving the trapping of a benzyne intermediate with a nitrile sulfide generated in situ by the reaction of dialkylaminothiazadiene, fluoride ion and trimethylsilyl fluoride is proposed.