Hypervalent Bromine(III) Compounds: Synthesis, Applications, Prospects

Winterson, Bethan; Patra, Tuhin; Wirth, Thomas

doi:10.1055/a-1675-8404

Cited by 16 publications

(12 citation statements)

References 64 publications

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“…Having succeeded in the formation of the six-membered bis-iodane 1 2+ , we sought to expand our study to rings incorporating two different halogen atoms. Indeed, despite a renewed spotlight on the organo-chloro(III) and -bromo(III) derivatives, , we could find no precedent of molecules having two distinct high-valent halogen atoms, let alone an example of a heterohalogen ring structure . Given that the synthetic route designed for 1 2+ was deemed unsuitable for hard-to-oxidize lighter halogens, an alternative retrosynthetic sequence was envisioned to access the six-membered bromine(III)–iodine(III) cycle.…”

Section: Resultsmentioning

confidence: 99%

Cyclic Homo- and Heterohalogen Di-λ³-diarylhalonium Structures

et al. 2023

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In the context of the ever-growing interest in the cyclic diaryliodonium salts, this work presents synthetic design principles for a new family of structures with two hypervalent halogens in the ring. The smallest bis-phenylene derivative, [(C6H4)2I2]2+, was prepared through oxidative dimerization of a precursor bearing the ortho-disposed iodine and trifluoroborate groups. We also report, for the first time, the formation of cycles containing two different halogen atoms. These present two phenylenes linked by hetero-(I/Br) or -(I/Cl) halogen pairs. This approach was also extended to the cyclic bis-naphthylene derivative [(C10H6)2I2]2+. The structures of these bis-halogen(III) rings were further assessed through X-ray analysis. The simplest cyclic phenylene bis-iodine(III) derivative features the interplanar angle of ∼120°, while a smaller angle of ∼103° was found for the analogous naphthylene-based salt. All dications form dimeric pairs through a combination of π–π and C–H/π interactions. As the largest member of the family, a bis-I(III)-macrocycle was also assembled using the quasi-planar xanthene backbone. Its geometry enables the two iodine(III) centers to be bridged intramolecularly by two bidentate triflate anions. In a preliminary manner, the interaction of the phenylene- and naphthalene-based bis-iodine(III) dications with a new family of rigid bidentate bis-pyridine ligands was studied in solution and the solid state, with an X-ray structure showing the chelating donor bonding to just one of the two iodine centers.

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Section: Resultsmentioning

confidence: 99%

Cyclic Homo- and Heterohalogen Di-λ³-diarylhalonium Structures

et al. 2023

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“…The chemistry of hypervalent halogen species has experienced tremendous progress in recent decades, with hypervalent iodine(III) compounds playing an increasingly important role in modern organic synthesis [1] . The related isoelectronic hypervalent bromine(III) reagents exhibit stronger electrophilicity, better nucleofugality of the bromanyl unit, and more driving force for oxidations, [2–4] as evidenced by a series of unprecedented synthetic transformations involving oxidative coupling of alkynes and primary alcohols to conjugated enones, [5] Hofmann rearrangement of sulfonamides to the corresponding N ‐arylsulfamoyl fluorides, [6] regioselective C−H functionalization of non‐activated alkanes, [7,8a] and a rare Bayer‐Villiger‐type oxidation of open‐chain aliphatic aldehydes [9] . Recently, the application of diaryl‐ λ 3 ‐bromanes in catalysis [10] and in cycloaddition reactions [11] was also reported.…”

Section: Introductionmentioning

confidence: 99%

Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds

Mohebbati

Sokolovs

Woite

et al. 2022

Chemistry A European J

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Hypervalent bromine(III) reagents possess a higher electrophilicity and a stronger oxidizing power compared to their iodine(III) counterparts. Despite the superior reactivity, bromine(III) reagents have a reputation of hard-to-control and difficult-to-synthesize compounds. This is partly due to their low stability, and partly because their synthesis typically relies on the use of the toxic and highly reactive BrF 3 as a precursor. Recently, we proposed chelation-stabilized hypervalent bromine(III) compounds as a possible solution to both problems. First, they can be conveniently prepared by electro-oxidation of the corresponding bromoarenes. Second, the chelation endows bromine(III) species with increased stability while retaining sufficient reactivity, comparable to that of iodine(III) counterparts. Finally, their intrinsic reactivity can be unlocked in the presence of acids. Herein, an in-depth mechanistic study of both the electrochemical generation and the reactivity of the bromine(III) compounds is disclosed, with implications for known applications and future developments in the field.

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“…The continuous microscopic exploration on the reaction mechanism of cyclic diaryliodonium enables the synthetic application of cyclic diaryliodonium salt to achieve greater value. The formation and reactivity of the novel cyclic iodolopyrazolium triflates and their isoelectronic iodine analogues needs in-depth study, [83][84][85][86][87][88][89] which provides facile access to a variety of biologically active compounds, drugs, chemicals, functional materials. There is a need for more research and development on the application of the enantioselective iodonium salts as halogen-bonding-donor organocatalysts to develop new asymmetrical reactions.…”

Section: Discussionmentioning

confidence: 99%

Cyclic Diaryliodonium Salts: Eco‐Friendly and Versatile Building Blocks for Organic Synthesis

Cheng

Guo

2023

Adv Synth Catal

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Cyclic diaryliodoniums are an important class of high‐valent aromatic iodine reagents for the synthesis of various axially chiral biaryls and biaryl compounds. Moreover, transition‐metal‐catalyzed annulation has been established for the construction of various heterocyclic rings and ladder‐type π‐conjugated polycyclic aromatic hydrocarbons with readily available cyclic diaryliodoniums as the starting materials. As halogen‐bonding donors, cyclic aryliodoniums have been explored as organocatalysts in a variety of organic reactions. In this review, the application progress of cyclic diaryliodoniums has been systematically outlined, which highlights recent developments in the application reactions of cyclic diaryliodoniums, including synthetic application, limitations and reaction mechanisms in representative cascade reactions to provide insights for the development prospects of cyclic diaryliodoniums.

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Hypervalent Bromine(III) Compounds: Synthesis, Applications, Prospects

Cited by 16 publications

References 64 publications

Cyclic Homo- and Heterohalogen Di-λ³-diarylhalonium Structures

Cyclic Homo- and Heterohalogen Di-λ³-diarylhalonium Structures

Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds

Cyclic Diaryliodonium Salts: Eco‐Friendly and Versatile Building Blocks for Organic Synthesis

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Hypervalent Bromine(III) Compounds: Synthesis, Applications, Prospects

Cited by 16 publications

References 64 publications

Cyclic Homo- and Heterohalogen Di-λ3-diarylhalonium Structures

Cyclic Homo- and Heterohalogen Di-λ3-diarylhalonium Structures

Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds

Cyclic Diaryliodonium Salts: Eco‐Friendly and Versatile Building Blocks for Organic Synthesis

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Cyclic Homo- and Heterohalogen Di-λ³-diarylhalonium Structures

Cyclic Homo- and Heterohalogen Di-λ³-diarylhalonium Structures