Organo‐Iodine(III)‐Catalyzed Oxidative Phenol–Arene and Phenol–Phenol Cross‐Coupling Reaction

Morimoto, Koji; Sakamoto, Kazuma; Ohshika, Takao; Dohi, Toshifumi; Kita, Yasuyuki

doi:10.1002/anie.201511007

Cited by 101 publications

(46 citation statements)

References 97 publications

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“…Carbon–carbon bond formation underpins almost every synthetic undertaking and oxidative processes that unite two nucleophilic partners, at the expense of a C−H bond in each partner, are at the forefront of synthetic technology. Such couplings are typically achieved using stoichiometric metals, or metal catalysts, however, metal‐free processes that do not rely on expensive metal catalysts, and do not generate metallic waste, are desirable …”

Section: Methodsmentioning

confidence: 99%

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The Interrupted Pummerer Reaction in a Sulfoxide‐Catalyzed Oxidative Coupling of 2‐Naphthols

Pulis

Procter

2019

Angew Chem Int Ed

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A benzothiophene S‐oxide catalyst, generated in situ by sulfur oxidation with H2O2, mediates the oxidative coupling of 2‐naphthols. Key to the catalytic process is the capture and inversion of reactivity of a 2‐naphthol partner, using an interrupted Pummerer reaction of an unusual benzothiophene S‐oxide, followed by subsequent coupling with a second partner. The new catalytic manifold has been showcased in the synthesis of the bioactive natural products, (±)‐nigerone and (±)‐isonigerone. Although Pummerer reactions are used widely, their application in catalysis is rare, and our approach represents a new catalytic manifold for metal‐free C−C bond formation.

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Section: Methodsmentioning

confidence: 99%

“…Adding the oxidant and activator in portions greatly improved reaction efficiencya nd product 2a was isolated in 84 %y ield (entry 2). Control experiments revealed that 3a' ', TFA, and TFAA were all essential for the reaction to proceed (entries [3][4][5]. Other terminal oxidants (e.g.…”

mentioning

confidence: 99%

The Interrupted Pummerer Reaction in a Sulfoxide‐Catalyzed Oxidative Coupling of 2‐Naphthols

Pulis

Procter

2019

Angew Chem Int Ed

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“…Another approach is the direct C−H activation by the means of chemical oxidizers to create the desired arylic C−C bond (Scheme ) . Recently, Kita and co‐workers reported an organo‐iodine(III)‐catalyzed pathway to access the desired cross‐coupling products . Unfortunately, this method is very tedious and needs Oxone™ as a terminal oxidant.…”

Section: Figurementioning

confidence: 99%

“…[10] Recently,K ita and co-workers reported an organo-iodine(III)-catalyzed pathway to access the desired cross-coupling products. [11] Unfortunately,this method is very tedious and needs Oxone as at erminal oxidant. Furthermore,t he reported scope for 4,4'-biphenols in that work was rather limited.…”

mentioning

confidence: 99%

Selective Formation of 4,4′‐Biphenols by Anodic Dehydrogenative Cross‐ and Homo‐Coupling Reaction

Dahms

Kohlpaintner

Wiebe

et al. 2019

Chemistry A European J

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A simple and selective electrochemical synthesis by dehydrogenative coupling of unprotected 2,6‐ or 2,5‐substituted phenols to the desired 4,4′‐biphenols is reported. Using electricity as the oxidizing reagent avoids pre‐functionalization of the starting materials, since a selective activation of the substrates takes place. Without the necessity for metal‐catalysts or the use of stoichiometric reagents it is an economic and environmentally friendly transformation. The elaborated electrochemical protocol leads to a broad variety of the desired 4,4′‐biphenols in a very simplified manner compared to classical approaches. This is particular the case for the cross‐coupled products.

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“…[ ][ ] However, this approach required a large excess of the arene and high temperatures, often resulting in regioisomeric mixtures of products and low functional group tolerance. More efficient processes were possible only in special cases, such as coupling with activated azoles or perfluorinated benzene rings. [ ][ ] Therefore, the availability of electrophilic indole or pyrrole synthons able to react with nucleophilic arene partners by C–H functionalization would tremendously enhance the range of accessible arylated heterocycles.…”

Section: Introductionmentioning

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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Organo‐Iodine(III)‐Catalyzed Oxidative Phenol–Arene and Phenol–Phenol Cross‐Coupling Reaction

Cited by 101 publications

References 97 publications

The Interrupted Pummerer Reaction in a Sulfoxide‐Catalyzed Oxidative Coupling of 2‐Naphthols

The Interrupted Pummerer Reaction in a Sulfoxide‐Catalyzed Oxidative Coupling of 2‐Naphthols

Selective Formation of 4,4′‐Biphenols by Anodic Dehydrogenative Cross‐ and Homo‐Coupling Reaction

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

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