Metal‐Free C−H Functionalization via Diaryliodonium Salts with a Chemically Robust Dummy Ligand

Chen, Yixuan; Gu, Yuefei; Meng, Huan; Shao, Qianzhen; Xu, Zhenchuang; Bao, Wenjing; Gu, Yu‐Cheng; Xue, Xiao‐Song; Zhao, Yanchuan

doi:10.1002/anie.202201240

Cited by 25 publications

(21 citation statements)

References 96 publications

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“…As an oxidizing salt, the most commonly employed DPI was utilized due to its favorable redox potential to oxidize free radicals to reactive cationic species [ 53 , 54 , 55 , 56 ]. Such photoinduced electron transfer reactions were already reported by several research groups [ 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 ].…”

Section: Introductionsupporting

confidence: 59%

Photoinitiated Cationic Ring-Opening Polymerization of Octamethylcyclotetrasiloxane

2023

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Photochemical techniques have recently been revitalized as they can readily be adapted to different polymerization modes to yield a wide range of complex macromolecular structures. However, the implementation of the photoinduced cationic methods in the polymerization of cyclic siloxane monomers has scarcely been investigated. Octamethylcyclotetrasiloxane (D4) is an important monomer for the synthesis of polydimethylsiloxane (PDMS) and its copolymers. In this study, the cationic ring-opening polymerization (ROP) of D4, initiated by diphenyl iodonium hexafluorophosphate (DPI), has been studied. Both direct and indirect initiating systems acting at broad wavelength using benzophenone and pyrene were investigated. In both systems, photochemically generated protonic acids and silylium cations are responsible for the polymerization. The kinetics of the polymerization are followed by viscosimetry and GPC analyses. The reported approach may overcome the problems associated with conventional methods and therefore represents industrial importance for the fabrication of polysiloxanes.

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Section: Introductionsupporting

confidence: 59%

Photoinitiated Cationic Ring-Opening Polymerization of Octamethylcyclotetrasiloxane

2023

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“…To demonstrate the utility of the developed diarylation methodology, it was evaluated in the synthesis of more complex products using functionalized diaryliodonium salts. Applications of heteroaryl iodonium salts are still scarce in arylation methodologies, [23] and a set of diverse heterocycle and complex scaffold-implanted iodonium salts were synthesized using literature methods. [24] They were applied in the present reaction conditions and pyridine-derived sulfide 3ag and coumarin-derived product 3ah were obtained in very high yields (Scheme 2B).…”

Section: Diarylation Of Sulfur Nucleophilesmentioning

confidence: 99%

Transition Metal-Free Difunctionalization of Sulfur Nucleophiles

Mondal

Tommaso

Olofsson

2022

Preprint

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Efficient protocols for accessing iodo-implanted diaryl and aryl(vinyl) thioethers have been developed using iodonium salts as reactive electrophilic arylation and vinylation reagents. The reactions take place under transition metal-free, thiol-free, and external base-free conditions. A wide variety of functional groups are tolerated in the S-diarylation, leading to the regioselective late-stage application of several heterocycles and drug molecules under mild reaction conditions. A novel S-difunctionalization pathway was discovered using vinyliodonium salts, which proceeds under additive-free reaction conditions and grants excellent stereoselectivity in the synthesis of (aryl)vinyl thioethers. A one-pot strategy combining transition metal-free diarylation and subsequent reduction provided facile access to electron-rich thioanilines and direct synthesis of a potential drug candidate derivative. The retained iodo group allows a wide array of further synthetic transformations. Mechanistic insights were elucidated by isolating the key intermediate, and the relevant energy profile was substantiated by DFT calculations.

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“…Structurally, aryliodonium salts can be classified into two categories: acyclic and cyclic aryliodoniums. Because of their high reactivity, air/moisture stability, and ready availability, acyclic aryliodoniums have been extensively utilized as efficient arylation reagents in organic synthesis. ,− For example, cross-coupling reactions involving acyclic aryliodoniums with carbonyl moieties, alkynes, alkenes, , and hetero atoms to construct various functionalized molecules − are realized. Compared to acyclic aryliodoniums, cyclic counterparts are less explored, although they could be employed for further transformations to set up a cascade reaction to achieve reaction economy.…”

Section: Introductionmentioning

confidence: 99%

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

et al. 2023

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Hypervalent aryliodoumiums are intensively investigated as arylating agents. They are excellent surrogates to aryl halides, and moreover they exhibit better reactivity, which allows the corresponding arylation reactions to be performed under mild conditions. In the past decades, acyclic aryliodoniums are widely explored as arylation agents. However, the unmet need for acyclic aryliodoniums is the improvement of their notoriously low reaction economy because the coproduced aryl iodides during the arylation are often wasted. Cyclic aryliodoniums have their intrinsic advantage in terms of reaction economy, and they have started to receive considerable attention due to their valuable synthetic applications to initiate cascade reactions, which can enable the construction of complex structures, including polycycles with potential pharmaceutical and functional properties. Here, we are summarizing the recent advances made in the research field of cyclic aryliodoniums, including the nascent design of aryliodonium species and their synthetic applications. First, the general preparation of typical diphenyl iodoniums is described, followed by the construction of heterocyclic iodoniums and monoaryl iodoniums. Then, the initiated arylations coupled with subsequent domino reactions are summarized to construct polycycles. Meanwhile, the advances in cyclic aryliodoniums for building biaryls including axial atropisomers are discussed in a systematic manner. Finally, a very recent advance of cyclic aryliodoniums employed as halogen-bonding organocatalysts is described.

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Metal‐Free C−H Functionalization via Diaryliodonium Salts with a Chemically Robust Dummy Ligand

Cited by 25 publications

References 96 publications

Photoinitiated Cationic Ring-Opening Polymerization of Octamethylcyclotetrasiloxane

Photoinitiated Cationic Ring-Opening Polymerization of Octamethylcyclotetrasiloxane

Transition Metal-Free Difunctionalization of Sulfur Nucleophiles

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

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