Reaction Of Diaryliodonium Salts Research Articles

A Thiol-Free Route to Alkyl Aryl Thioethers.

Most existing methods for the synthesis of alkyl aryl thioethers require the use of mercaptans as the starting materials, which comes with practical limitations. Reactions of diaryliodonium salts with xanthate salts, easily prepared from the corresponding alcohols and CS2, under the developed conditions represent an operationally simple, thiol-free method for the synthesis of these valuable compounds. The protocol features high functional group tolerance and can be applied to the late-stage C-H functionalization and for the introduction of a CD3S group.

Reaction of Diaryliodonium Salts with Potassium Alkyl Xanthates as an Entry Point to Accessing Organosulfur Compounds.

Preparation of S-aryl xanthates via transition-metal-catalyzed or SNAr reactions is complicated by their further transformations under the utilized conditions. In contrast, S-arylation of potassium O-alkyl xanthates with diaryliodonium salts proceeds under mild conditions, enabling access to substituted S-aryl xanthates. The method exhibits good functional group tolerance and can be applied to the late-stage C-H functionalization of drug molecules. Divergent transformations of the resulting S-aryl xanthates provide rapid access to a range of medicinal chemistry-relevant organosulfur compounds.

Concise synthesis of xanthones by the tandem etherification—Acylation of diaryliodonium salts with salicylates

An efficient synthetic method for multi-substituted xanthones was developed. The reaction of diaryliodonium salts and salicylates was employed for the preparation of the xanthones. This method proceeded through an intermolecular etherification-acylation to give target heterocycles in good yields (up to 91%). Multi-substituted xanthones were gained by shifting the substituent of salicylates or diaryliodonium salts

Copper-mediated trifluoromethylation of diaryliodonium salts with difluoromethyltriflate

Abstract The reaction of diaryliodonium salts with difluoromethyltriflate in the presence of TBAT and CuTC gave the corresponding trifluoromethylated arenes in moderate yields. Compared to other difluorocarbene-derived trifluoromethylation reactions, the current one proceeded at mild reaction conditions (room temperature) within short reaction time (5 min).

Copper-mediated trifluoromethylation of diaryliodonium salts with TMSCF3 at room temperature

Abstract A convenient method for the preparation of trifluoromethylated arenes from the reaction of diaryliodonium salts with TMSCF3 in the presence of CuBF4·(MeCN)4 and KF at room temperature within 25 min was developed. This reaction provides a valuable complement to the previously established trifluoromethylation methods.

ChemInform Abstract: Synthesis of Phenanthridine Derivatives via Cascade Annulation of Diaryliodonium Salts and Nitriles.

A cascade coupling reaction toward a variety of phenanthridine derivatives has been developed. This cascade transformation proceeds via the copper-catalyzed coupling reaction of diaryliodonium salts and nitriles, and undergoes cyclization into the phenanthridine core.

ChemInform Abstract: One‐Pot Synthesis of Multiply Substituted Quinoline and Quinazoline Derivatives via [2 + 2 + 2] Cascade Annulation with Diaryliodonium Salts.

AbstractA facile protocol is presented for the three‐component reaction of diaryliodonium salts with nitriles and alkynes to give a wide variety of quinoline derivatives.

ChemInform Abstract: Cu‐Catalyzed Couplings of Aryl Iodonium Salts with Sodium Trifluoromethanesulfinate.

A convenient method for the preparation of aryl trifluoromethylsulfones from the reactions of diaryliodonium salts with sodium trifluoromethanesulfinate in the presence of copper catalysts is described. Cuprous oxide in DMF was found to be the optimal catalyst for the reaction. The reaction conditions are tolerant of various functional groups as well as of various counteranions of the iodonium salt. The synthetic utility of the process is demonstrated by performing the reaction on a preparative scale (88 g).

Cu-Catalyzed Couplings of Aryl Iodonium Salts with Sodium Trifluoromethanesulfinate

A convenient method for the preparation of aryl trifluoromethylsulfones from the reactions of diaryliodonium salts with sodium trifluoromethanesulfinate in the presence of copper catalysts is described. Cuprous oxide in DMF was found to be the optimal catalyst for the reaction. The reaction conditions are tolerant of various functional groups as well as of various counteranions of the iodonium salt. The synthetic utility of the process is demonstrated by performing the reaction on a preparative scale (88 g).

Applications of iodonium salts and iodonium ylides as precursors for nucleophilic fluorination in Positron Emission Tomography

This review summarizes the applications of iodonium compounds in the rapidly developing field of Positron Emission Tomography (PET). Reactions of diaryliodonium salts with fluoride anion have found wide practical application in PET as a fast and convenient method for the introduction of the radioactive ( 18 F)-fluoride into radiotracer molecules. The best synthetic methods for the preparation of iodonium precursors for PET are described, the mechanistic aspects of nucleophilic fluorination reaction are discussed, and specific examples of the preparation of PET radioligands are provided.

Single‐Step Radiosynthesis of “18F‐Labeled Click Synthons” from Azide‐Functionalized Diaryliodonium Salts

Positron emission tomography (PET) is an increasingly important biomedical imaging technique that relies on the development of radiotracers labeled with positron-emitters to achieve biochemical specificity. Fluorine-18 (t1/2 = 109.7 min) is an attractive positron-emitting radiolabel for organic radiotracers, primarily because of its longer half-life and greater availability relative to those for the main alternative, carbon-11 (t1/2 = 20.4 min). Rapid simple methods are sought for labeling prospective PET radiotracers with fluorine-18 from cyclotron-produced aqueous [18F]fluoride ion, which must often be converted first into a suitably reactive labeling synthon for use in a subsequent labelling reaction. Use of 18F-labeled synthons in 'click chemistry' attracts increasing attention for labeling PE Tradiotracers. Here we describe rapid single-step radiosyntheses of azido- or azidomethyl-bearing [18F]fluoroarenes from the reactions of diaryliodonium salts with no-carrier-added [18F]fluoride ion within a microfluidic apparatus to provide previously poorly accessible 18F-labeled click synthons in radiochemical yields of 15% for [18F]4-fluorophenyl azide and about 40% for each of the [18F](azidomethyl)-fluorobenzenes. The radiosyntheses of the latter synthons was possible under 'wet conditions', so obviating the need to dry the cyclotron-produced [18F]fluoride ion and greatly enhancing the practicality of the method.

HYPERVALENT IODINE IN SYNTHESIS 55: AN EFFICIENT METHOD FOR SYNTHESIS OF ARYL SULFIDES BY PALLADIUM-CATALYZED REACTION OF HYPERVALENT IODONIUM SALTS WITH MERCAPTANS

The synthesis of aryl sulfides was carried out in high yields by the palladium-catalyzed cross-coupling reaction of diaryliodonium salts with mercaptans at room temperature in THF.

HYPERVALENT IODINE IN SYNTHESIS. 52. PALLADIUM- CATALYZED ARYLATION OF O,O-DIALKYL PHOSPHITES WITH DIARYLIODONIUM SALTS: A CONVENIENT METHOD FOR SYNTHESIS OF ARYLPHOSPHONATES

Palladium-catalyzed coupling reaction of diaryliodonium salts with O,O-dialkyl phosphites gave arylphosphonates in good yields.

Hypervalent Iodine in Synthesis 47: Cross-Coupling Reaction of Diaryliodonium Salts with Grignard Reagents via a Novel Double Metal Co-Catalyst

The cross-coupling of diaryliodonium salts with Grignard reagents in the presence of ZnCl2 and a palladium catalyst afforded biaryls under mild conditions and in good yields.

Hypervalent Iodine in Synthesis XXX: Palladium-Catalyzed Reaction of Diaryliodonium Salts with β-substituted-α, β-enones

The reaction of diaryliodonium salts with β-substituted-α,β-enones in the presence of a palladium catalyst affords Hβ-substituted products with excellent yields.

Palladium-Catalyzed Cross-Coupling of Organozirconium Compounds with Diaryliodonium Salts

The palladium-catalyzed cross-coupling reaction of diaryliodonium salts with organozirconium compounds was achieved for about 1–1.5 hrs at room temperature and the reaction proceeded with retention of configuration to provide a new convenient method for the synthesis of (E)-disubstituted alkenes.

Hypervalent Iodine in Synthesis: XII. A New and Convenient Method for Preparation of O,O-Dialkyl S-Aryl Phosphoro Thiolates

Abstract O, O-Dialkyl S-aryl phosphorothiolates have been prepared in better yields by the reaction of diaryliodonium salts with potassium O, O-dialkyl phosphorothiolates in cyclohexane at reflux temperature.

Conversion of diaryliodonium salts to aryl fluorides

The preparation of aryl fluorides by the reaction of diaryliodonium salts with KF is discussed. Generally, best results were obtained when the salt Ar 2I +X − was heated with KF in the absence of solvent. The counterion, X −, must be non-nucleophilic.

Kinetics of the reactions of diabyliodonium salts with mercury

1. A study has been made of the kinetics of the reactions of diaryliodonium salts with metallic mercury in acetonitrile solution. 2. The reactions of the diaryliodonium chlorides with mercury are insensitive to changes in the substituent in the benzene ring of the iodonium salt. 3. A study has also been made of the temperature variation of the rates of decomposition of diphenyliodonium chlorides and bromides under the action of mercury in acetonitrile solution. Activation parameters have been obtained for these reactions. 4. Discussion is given of possible mechanisms for the reactions of these salts with mercury.