Arylphosphonylation and Arylazidation of Activated Alkenes

Kong, Wangqing; Merino, Estı́baliz; Nevado, Cristina

doi:10.1002/anie.201311241

Cited by 255 publications

(83 citation statements)

References 91 publications

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“…Initially, the in situ -generated nitrogen-centred radical A added to the triple bond of alkyne (for example 6g ) regioselectively, providing a highly reactive vinyl radical B . Subsequently, sequential intramolecular 1,4-aryl migration via 5- ipso cyclization and desulfonylation would produce amidyl radical C 58 59 60 61 . This imidyl radical exists at an equilibrium with its resonance structure α-imino carbon radical D which could be stabilized by two aromatic rings and a C=N double bond.…”

Section: Resultsmentioning

confidence: 99%

Radical cascade reaction of alkynes with N-fluoroarylsulfonimides and alcohols

et al. 2015

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Cascade reactions initiated by radical addition to alkynes are synthetically very attractive because they enable access to highly complex molecular skeletons in only few synthetic steps under usually mild conditions. Here we report a general radical cascade reaction of alkynes, N-fluoroarylsulfonimides and alcohols, enabling the efficient synthesis of important α-amino-α-aryl ketones from readily available starting materials via a single operation. During this process, the highly regioselective nitrogen-centred radical addition to internal and terminal alkynes generating vinyl radicals and the next explicit migration of aryl group from the nitrogen source lead the following efficient desulfonylation, oxygenation, and semi-pinacol rearrangement. In addition, the semi-pinacol rearrangement precursors, α-alkyloxyl-α,α-diaryl imines, could also be efficiently obtained under milder conditions. This methodology might open a new entry for designing intermolecular radical cascade reaction of alkynes.

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Section: Resultsmentioning

confidence: 99%

Radical cascade reaction of alkynes with N-fluoroarylsulfonimides and alcohols

et al. 2015

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“…[33] They developed the arylazidation of acrylamides based on the internal transfer of an aryl group on a sulfonamide (Scheme 8). -Azido amides 55-57 bearing an all-carbon quaternary center in -position were obtained in 72-75% yield.…”

Section: C-n Bond Formationmentioning

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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“…Using different amount of AgNO 3, α-aryl-β-phosphinoyl amides 280 and phosphonyl oxindoles 281 could be generated selectively. The reaction of N-methyl-N-tosyl amide 282 furnished spiro compound 284 through the formation of radical 283 in the presence of an increased amount of AgNO 3 (Scheme 119) 208. …”

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confidence: 99%