Iodonium Metathesis Reactions

Kasahara, Takahito; Jang, Young Jin; Racicot, Léanne; Panagopoulos, Dimitrios; Liang, Steven H.; Ciufolini, Marco A.

doi:10.1002/anie.201405594

Cited by 26 publications

(12 citation statements)

References 27 publications

(5 reference statements)

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“…All diaryliodonium salts 2 have been reported previously, and their spectral data match the literature values for 2a , 2b , 2c , 2d , 2e , 2f , 2g , 2h , 2i , 2j , 2k , and 2n …”

Section: Methodssupporting

confidence: 83%

Synthesis of N-(2-Hydroxyaryl)benzotriazoles via Metal-Free O-Arylation and N–O Bond Cleavage

Wang

Shi

et al. 2016

J. Org. Chem.

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A metal-free method for synthesis of N-(2-hydroxyaryl)benzotriazoles via O-arylation of N-hydroxybenzotriazoles with readily available diaryliodonium salts and sequential N-O bond cleavage under mild conditions has been developed. The [3,3]-rearrangement of N-O bond cleavage could take place on the N instead of C atom. The reaction was compatible with diverse functional groups and a new type of P,N-ligand was synthesized in three steps.

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“…All diaryliodonium salts 2 have been reported previously, and their spectral data match the literature values for 2a , 2b , 2c , 2d , 2e , 2f , 2g , 2h , 2i , 2j , 2k , and 2n …”

Section: Methodssupporting

confidence: 83%

Synthesis of N-(2-Hydroxyaryl)benzotriazoles via Metal-Free O-Arylation and N–O Bond Cleavage

Wang

Shi

et al. 2016

J. Org. Chem.

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“…So far, numerous applications of hypervalent halogens, mostly hypervalent iodine, have been explored. Whereas iodine(III) and iodine(V) have been extensively studied, little is known about halogen(I) intermediates owing to their unstable nature. Moreover, systematic accounts focusing on their reactivity upon interaction with Lewis bases are rare.…”

Section: Introductionmentioning

confidence: 99%

Role of Lewis‐Base‐Coordinated Halogen(I) Intermediates in Organic Synthesis: The Journey from Unstable Intermediates to Versatile Reagents

et al. 2017

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The widespread use of halogen‐based reagents in organic synthesis is well known. Hypervalent halogens (oxidation states III and V) have been explored to a significant extent. Among them, hypervalent iodine reagents have found major use and applications. In contrast, understanding of the reactivity of halogen(I) species in the presence of Lewis bases, and their reaction mechanisms, are very limited. This microreview sheds light on the importance of halogen(I) species and their applications in organic synthesis. In commercially available halogen(I) precursors such as N‐halosuccinimides, the halogen atom is attached to the nitrogen atom through a covalent bond with low electrophilicity and thus low reactivity. Interestingly, the reactivity increases if the electrophilic halogen(I) atom is attached to a Lewis base through a polarized covalent bond. The halogen‐bonding interaction between the Lewis base and the halonium ion (or halonium ion equivalent) results in highly reactive and thermodynamically stable halogen(I) intermediates that act as versatile reagents. This microreview unravels the evolution of the unstable halogen(I) intermediates to become versatile reagents.

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“…ThiopheneBX 45 and DimethylFuranBX 46 were also synthesized in low to moderate yield. In this case, the corresponding iodonium salts are already known and have been applied in catalytic transformations …”

Section: Resultsmentioning

confidence: 99%

Bench‐Stable Electrophilic Indole and Pyrrole Reagents: Serendipitous Discovery and Use in C–H Functionalization

Caramenti

Waser

2017

Helvetica Chimica Acta

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The development of reagents allowing the reversal of the standard reactivity (Umpolung) of small building blocks is an important field of research in chemistry, as it allows increasing the flexibility of organic synthesis. Indoles and pyrroles are ubiquitous heterocycles in natural products and drugs. They are usually functionalized making use of their high nucleophilicity. In contrast, only few methods are based on the use of electrophilic indole and pyrrole synthons, as the needed reagents are highly unstable or can be used only with a very narrow scope. Herein, we report the serendipitous discovery and first use in the C–H functionalization of arenes of IndoleBX and PyrroleBX, new thermally highly stable benziodoxol(on)e hypervalent iodine reagents. IndoleBX and PyrroleBX could be obtained in one step from the corresponding heterocycles and acetoxy benziodoxolone using a Lewis acid catalyst. The mild reactions conditions allowed the introduction of a broad range of functional groups, including ethers, halogens and boronic esters. The new reagents could then be used in the rhodium‐ and ruthenium‐catalyzed C–H heteroarylation of arene rings bearing heterocyclic or benzamide directing groups. Such transformations could not be realized using previously reported C–H functionalization procedures.

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Iodonium Metathesis Reactions

Abstract: A metathesis reaction occurs when a diaryliodonium triflate is heated with an aryl iodide, resulting in formation of a new diaryliodonium triflate.

Cited by 26 publications

References 27 publications

Synthesis of N-(2-Hydroxyaryl)benzotriazoles via Metal-Free O-Arylation and N–O Bond Cleavage

Synthesis of N-(2-Hydroxyaryl)benzotriazoles via Metal-Free O-Arylation and N–O Bond Cleavage

Role of Lewis‐Base‐Coordinated Halogen(I) Intermediates in Organic Synthesis: The Journey from Unstable Intermediates to Versatile Reagents

Bench‐Stable Electrophilic Indole and Pyrrole Reagents: Serendipitous Discovery and Use in C–H Functionalization

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