Remote Substituents as Potential Control Elements for the Solid-State Structures of Hypervalent Iodine(III) Compounds

Li, Guobi; Rheingold, Arnold L.; Protasiewicz, John D.

doi:10.1021/acs.inorgchem.1c00339

Cited by 7 publications

(3 citation statements)

References 86 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…More recently, hypervalent iodine compounds containing multiple iodine(III) centers have drawn interest for applications as material precursors, supramolecular materials, and bidentate Lewis acids. , Stang and co-workers have reported a series of macrocyclic aryliodoniums in which multiple iodine(III) atoms bridge the biaryl together, for example, compounds 29 and 30 , (Scheme A). These macrocyclic aryliodoniums are more like acyclic.…”

Section: Advance In Design and Synthesis Of Cyclic Aryliodoniumsmentioning

confidence: 99%

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

et al. 2023

View full text Add to dashboard Cite

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.

show abstract

Section: Advance In Design and Synthesis Of Cyclic Aryliodoniumsmentioning

confidence: 99%

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

et al. 2023

View full text Add to dashboard Cite

show abstract

“…The supramolecular architectures most frequently adopted by I III -based species have been highlighted in reviews and book considerations. − Diaryliodonium salts (a subclass of λ 3 -iodanes) function as double-σ-hole donors and comprise a class of promising tectons for the preparation of novel supramolecular arrays exhibiting useful functional properties, e.g., of halogen bonded organic frameworks (the so-called XOFs) with permanent porosity. ,− Analysis of the Cambridge Structural Database (CSD) revealed that heterotetrameric adducts (0D architectures) are the most common supramolecular arrangement formed by diaryliodonium salts regardless of the used anion, while 1D chains are much less abundant arrays (Figure A,C).…”

Section: Introductionmentioning

confidence: 99%

Controlled Halogen-Bond-Involving Assembly of Double-σ-Hole-Donating Diaryliodonium Cations and Ditopic Arene Sulfonates

Soldatova

Suslonov

Ivanov

et al. 2022

Crystal Growth & Design

View full text Add to dashboard Cite

The supramolecular dimensionality of halogen bonded architectures formed in the solid state by diaryliodonium salts is greater when the anion is a disulfonate rather than a monosulfonate. Specifically, diaryliodonium cations conventionally function as double-σ-hole halogen bond (XB) donors and form 0D-heterotetrameric motifs when paired with monosulfonate anions. Here it is reported that when 1,5-and 2,6-naphthalenedisulfonate anions are used as ditopic XB acceptors, their assemblies with diaryliodonium cations provide architectures of higher dimensionality. 1,5-Naphthalenedisulfonate leads to the occurrence of 1D chains, while the longer and less sterically encumbered 2,6-naphthalenedisulfonate produces either 1D chains or 2D layers. The two-center I•••OSO supramolecular synthon is observed most frequently, and the three-center I•••OSO linkage was identified in some assemblies based on 2,6naphthalenedisulfonate.

show abstract

“…25 We have recently reported on crystal structural analyses of para-donor-substituted ArI(OAc)2 and their associated intra-and inter-molecular I•••O interactions, with the goal of rationally designed supramolecular materials. 26 These studies revealed that intramolecular I•••O interactions from the vicinal carbonyl oxygen atoms of the carboxylate groups tended to block access to the iodine(III) centers from prospective electron rich donor groups of neighboring molecules. Cyclic iodonium ylides thus offered the opportunity to examine HVI compounds free of interference of the directly bound carboxylate groups.…”

Section: Introductionmentioning

confidence: 99%

Solid state aggregation of cyclic iodonium ylides

Protasiewicz¹,

Li²,

Rheingold³

2021

Arkivoc

Self Cite

View full text Add to dashboard Cite

Iodonium ylides (ArI=CR(R")) represent unusual hypervalent iodine(III) sources of carbene equivalents. While their reactivity is well-described, their detailed structural chemistry is somewhat limited due to their thermal instability. Cyclic iodonium ylides typically have greater thermal stability than acyclic ylides, but so far few such materials have been examined by single crystal X-ray diffraction methods. This report details the synthesis of two cyclic iodonium ylides and their association in the solid state by intermolecular I•••O interactions.

show abstract

Remote Substituents as Potential Control Elements for the Solid-State Structures of Hypervalent Iodine(III) Compounds

Cited by 7 publications

References 86 publications

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

Controlled Halogen-Bond-Involving Assembly of Double-σ-Hole-Donating Diaryliodonium Cations and Ditopic Arene Sulfonates

Solid state aggregation of cyclic iodonium ylides

Contact Info

Product

Resources

About