Synthesis and structural characterization of nitro-functionalized cyclic hypervalent iodine compounds

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

doi:10.1016/j.poly.2022.115988

Cited by 5 publications

(6 citation statements)

References 44 publications

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“…Chemical structures of some diaryliodonium salts (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16) in this study, Mes, mesitylene.…”

Section: S C H E M Ementioning

confidence: 85%

“…[1][2][3] The notable feature of HICs is their ability to exhibit similar reactivity to the transition metal reagents due to the changes in valence states, thereby providing cost-effective alternatives to expensive organometallic catalysts and toxic heavy metal-based oxidants. 4,5 Within this category of HICs, diaryliodonium salts, also referred to as diaryl-λ 3 -iodines, following IUPAC nomenclature, 6 stand out as a unique class of HICs renowned for their utility as highly electrophilic arylating reagents under mild reaction conditions. 7 Apart from their synthetic applications, diaryliodonium salts play a significant role in semiconductor photolithography.…”

Section: Introductionmentioning

confidence: 99%

“…Hypervalent iodine compounds (HICs) possess remarkable advantageous characteristics, including facile synthesis, low toxicity, and environmental friendliness, making them versatile tools in a wide range of organic reactions, such as functionalizations, rearrangements, aryl‐coupling, and cyclization reactions 1–3 . The notable feature of HICs is their ability to exhibit similar reactivity to the transition metal reagents due to the changes in valence states, thereby providing cost‐effective alternatives to expensive organometallic catalysts and toxic heavy metal‐based oxidants 4,5 . Within this category of HICs, diaryliodonium salts, also referred to as diaryl‐λ 3 ‐iodines, following IUPAC nomenclature, 6 stand out as a unique class of HICs renowned for their utility as highly electrophilic arylating reagents under mild reaction conditions 7 .…”

Section: Introductionmentioning

confidence: 99%

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Gas‐phase Smiles rearrangement of ortho‐nitro‐substituted diaryliodonium cations and their mechanistic insights

Wei,

Pan,

Ling

et al. 2024

Rapid Comm Mass Spectrometry

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RationaleDiaryliodonium salts are useful electrophilic reagents in organic chemistry, finding extensive applications in arylations and photo‐induced polymerizations. However, comprehensive mechanistic investigations, particularly concerning the mass spectrometric behaviors of diaryliodonium salts, are relatively scarce in the literature.MethodsDiaryliodonium salts could be readily ionized using electrospray ionization mass spectrometry (ESI‐MS) to give [Ar1‐I+‐Ar2], and high‐resolution ESI‐tandem mass spectrometry (MS/MS) experiments were conducted to investigate their gas‐phase chemical reactions.ResultsInvestigations on ESI‐MS/MS of [Ar1‐I+‐Ar2] revealed two major fragmentation patterns: (1) reductive elimination resulting in the diaryl coupling product ion [Ar1‐Ar2]+• by the loss of I; (2) generation of aryl cations [Ar1]+ or [Ar2]+ through cleavage of the C–I bonds. We revealed that the introduction of NO2 into Ar2 of [Ar1‐I+‐Ar2] could lead to an unexpected fragmentation ion [Ar1O]+ in MS/MS, arising from an O‐atom transfer process from NO2 to Ar1. Particularly, when NO2 was ortho‐positioned to the iodine in Ar2, the [Ar1O]+ sometimes exhibited dominant behavior.ConclusionsComprehensive ESI‐MS/MS studies and theoretical calculations provided strong support for the O‐atom transfer mechanistic pathway: [Ar1‐I+‐(o‐NO2‐Ar2)] initially underwent a Smiles rearrangement to the intermediate [Ar1‐O‐(o‐NO‐Ar2I)]+, which subsequently dissociated to [Ar1O]+ or [o‐NO‐Ar2I]+•. Herein, we proposed an unexpected “ortho effect” in the gas‐phase fragmentation reaction of [Ar1‐I+‐(o‐NO2‐Ar2)], in which the crucial determinant factor for the aryl migration was identified as the Smiles rearrangement reaction.

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“…Chemical structures of some diaryliodonium salts (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16) in this study, Mes, mesitylene.…”

Section: S C H E M Ementioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Gas‐phase Smiles rearrangement of ortho‐nitro‐substituted diaryliodonium cations and their mechanistic insights

Wei,

Pan,

Ling

et al. 2024

Rapid Comm Mass Spectrometry

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“…Furthermore, they have been used as halogen‐bonding organocatalysts, [10] and dibenziodolium chloride (diphenyleneiodonium, DPI) is commonly used in biological studies [11] . The structures of several types of cyclic iodonium salts have also been investigated [8d,12] …”

Section: Introductionmentioning

confidence: 99%

“… [11] The structures of several types of cyclic iodonium salts have also been investigated. [ 8d , 12 ]…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Cyclic and Acyclicortho‐Aryloxy Diaryliodonium Salts for Chemoselective Functionalizations

Linde

Knippenberg

Olofsson

2022

Chemistry A European J

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Two regioselective, high-yielding one-pot routes to oxygen-bridged cyclic diaryliodonium salts and ortho-aryloxysubstituted acyclic diaryliodonium salts are presented. Starting from easily available ortho-iodo diaryl ethers, complete selectivity in formation of either the cyclic or acyclic product could be achieved by varying the reaction conditions. The complimentary reactivities of these novel ortho-oxygenated iodonium salts were demonstrated through a series of chemoselective arylations under metal-catalyzed and metalfree conditions, to deliver a range of novel, ortho-functionalized diaryl ether derivatives.

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Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Yoshimura,

Zhdankin

2024

Chem. Rev.

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Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. Hypervalent iodine reagents are commonly used in synthetically important halogenations, oxidations, aminations, heterocyclizations, and various oxidative functionalizations of organic substrates. Iodonium salts are important arylating reagents, while iodonium ylides and imides are excellent carbene and nitrene precursors. Various derivatives of benziodoxoles, such as azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, and alkenylbenziodoxoles have found wide application as group transfer reagents in the presence of transition metal catalysts, under metal-free conditions, or using photocatalysts under photoirradiation conditions. Development of hypervalent iodine catalytic systems and discovery of highly enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important recent achievement in the field of hypervalent iodine chemistry. Chemical transformations promoted by hypervalent iodine in many cases are unique and cannot be performed by using any other common, non-iodine-based reagent. This review covers literature published mainly in the last 7−8 years, between 2016 and 2024.

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Synthesis and structural characterization of nitro-functionalized cyclic hypervalent iodine compounds

Cited by 5 publications

References 44 publications

Gas‐phase Smiles rearrangement of ortho‐nitro‐substituted diaryliodonium cations and their mechanistic insights

Gas‐phase Smiles rearrangement of ortho‐nitro‐substituted diaryliodonium cations and their mechanistic insights

Synthesis of Cyclic and Acyclicortho‐Aryloxy Diaryliodonium Salts for Chemoselective Functionalizations

Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

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