Room-temperature Cu(<scp>ii</scp>)-catalyzed aromatic C–H azidation for the synthesis of ortho-azido anilines with excellent regioselectivity

Fan, Yunpeng; Wan, Wen; Ma, Guobin; Gao, Wei; Jiang, Haizhen; Zhu, Shizheng; Hao, Jian

doi:10.1039/c4cc01481b

Cited by 95 publications

(43 citation statements)

References 37 publications

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“…[34b] In 2014, two research groups reported the combination of copper catalysis with benziodoxolone 9 for the azidation of electron-rich aromatic compounds (Scheme 10). [35] Jiao and co-workers developed the azidation of skatole derivatives in the presence of alcohols to give dehydroindole derivatives (Scheme 10 A). [35a] Intramolecular attack of an alcohol to give indoline derivatives was also possible.H ao and co-workers reported the ortho azidation of anilines at room temperature (Scheme 10 B).…”

Section: Methodsmentioning

confidence: 99%

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

et al. 2016

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Hypervalent iodine compounds are privileged reagents in organic synthesis because of their exceptional reactivity. Among these compounds, cyclic derivatives stand apart because of their enhanced stability. They have been widely used as oxidants, but their potential for functional‐group transfer has only begun to be investigated recently. The use of benziodoxol(on)es for trifluoromethylation (Togni's reagents) is already widely recognized, but other transformations have also attracted strong interest recently. In this Review, the development in the area since 2011 will be presented. After a short summary of synthetic methods to prepare benziodoxol(on)e reagents, their use to construct carbon–heteroatom and carbon–carbon bonds will be presented. In particular, the introduction of alkynes by using ethynylbenziodoxol(on)e (EBX) reagents has been highly successful. Breakthroughs in the introduction of alkoxy, azido, difluoromethyl, and cyano groups will also be described.

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Section: Methodsmentioning

confidence: 99%

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

et al. 2016

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“…In recent years, hypervalent iodine reagents have emerged as environmentally friendly and efficient oxidizing reagents for various synthetically useful oxidative transformations 1. Particularly important are hypervalent iodine(III) compounds with iodinenitrogen bonds,2 such as azidoiodanes,2a–e benziodazoles,2f, g amidobenziodoxoles,2j and iminoiodanes,2j–o all of which are efficient reagents for CN bond forming reactions. Representative recent examples of synthetic applications of these reagents include direct azidation, amination, imidation, aziridination, metal‐catalyzed imidation, and CH insertion reactions 2.…”

Section: Methodsmentioning

confidence: 99%

Saccharin‐Based μ‐Oxo Imidoiodane: A Readily Available and Highly Reactive Reagent for Electrophilic Amination

Yoshimura

Koski

Fuchs

et al. 2015

Chemistry A European J

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Three new saccharin-based hypervalent iodine compounds were prepared by the reaction of saccharine with (diacetoxyiodo)arenes or acetoxybenziodoxole. Structures of these new imidoiodanes were established by X-ray crystallography. The saccharin-based μ-oxo-bridged imidoiodane readily reacts with silyl enol ethers under mild conditions to give the corresponding α-aminated carbonyl compounds in moderate yields.

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“…Hao and co‐workers demonstrated in 2014 that Cu II can also be used to activate ortho ‐C–H bonds in anilines to give o ‐azido anilines . The difference from the protocol reported by Jiao and described above is that azidobenziodoxoles were used as the azide source instead of TMSN 3 , circumventing the need for an external oxidant.…”

Section: Base‐metal‐catalysed Azidation Reactionsmentioning

confidence: 99%

Metal‐Catalysed Azidation of Organic Molecules

Goswami

Bruin

2016

Eur J Org Chem

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The azide moiety is a desirable functionality in organic molecules, useful in a variety of transformations such as olefin aziridination, C–H bond amination, isocyanate synthesis, the Staudinger reaction and the formation of azo compounds. To harness the versatility of the azide functionality fully it is important that these compounds be easy to prepare, in a clean and cost‐effective manner. Conventional (non‐catalysed) methods to synthesise azides generally require quite harsh reaction conditions that are often not tolerant of functional groups. In the last decade, several metal‐catalysed azidations have been developed in attempts to circumvent this problem. These methods are generally faster, cleaner and more functional‐group‐tolerant than conventional methods to prepare azides, and can sometimes even be conveniently combined with one‐pot follow‐up transformations of the installed azide moiety. This review highlights metal‐catalysed approaches to azide synthesis, with a focus on the substrate scopes and mechanisms, as well as on advantages and disadvantages of the methods. Overall, metal‐catalysed azidation reactions provide shorter routes to a variety of potentially useful organic molecules containing the azide moiety.

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Room-temperature Cu(ii)-catalyzed aromatic C–H azidation for the synthesis of ortho-azido anilines with excellent regioselectivity

Abstract: Cu(ii)-catalyzed aromatic C-H azidation with azido-benziodoxolone under mild conditions has been described. The primary amine exhibits an excellent ortho-directing effect, providing ortho-azidated anilines as the sole products.

Cited by 95 publications

References 37 publications

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

Saccharin‐Based μ‐Oxo Imidoiodane: A Readily Available and Highly Reactive Reagent for Electrophilic Amination

Metal‐Catalysed Azidation of Organic Molecules

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