Silver-Catalyzed Radical Aminofluorination of Unactivated Alkenes in Aqueous Media

Li, Zhaodong; Song, Liyan; Li, Chaozhong

doi:10.1021/ja400124t

Cited by 321 publications

(125 citation statements)

References 67 publications

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“…Ritter and co-workers proposed recently the presence of bimetallic aryl-Ag(II)-Ag(II)-F species in silver(I)-mediated electrophilic fluorination of aryl stannanes 14 . Instead, Li and co-workers suggest in their studies on Ag(I)-catalysed radical aminofluorinations that electrophilic fluoride sources are capable of generating monometallic Ag(III)-F intermediate species 28 , although the C-F bond formation is proposed to occur through reaction of a Ag(II)-F and a carbon-centred radical species, following a one-electron redox sequence. No direct evidence of the intermediates proposed is reported, thus mechanistic comprehension of silver-catalysed processes stands as its Achilles heel for future design of new synthetic methodologies.…”

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confidence: 99%

Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

et al. 2014

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Silver is extensively used in homogeneous catalysis for organic synthesis owing to its Lewis acidity, and as a powerful one-electron oxidant. However, two-electron redox catalytic cycles, which are most common in noble metal organometallic reactivity, have never been considered. Here we show that a Ag(I)/Ag(III) catalytic cycle is operative in model C–O and C–C cross-coupling reactions. An aryl-Ag(III) species is unequivocally identified as an intermediate in the catalytic cycle and we provide direct evidence of aryl halide oxidative addition and C–N, C–O, C–S, C–C and C–halide bond-forming reductive elimination steps at monometallic silver centres. We anticipate our study as the starting point for expanding Ag(I)/ Ag(III) redox chemistry into new methodologies for organic synthesis, resembling well-known copper or palladium cross-coupling catalysis. Furthermore, findings described herein provide unique fundamental mechanistic understanding on Ag-catalysed cross-coupling reactions and dismiss the generally accepted conception that silver redox chemistry can only arise from one-electron processesThis work was supported by grants from the European Research Council (Starting Grant Project ERC-2011-StG-277801), the Spanish MINECO (CTQ2012-37420-C02-01/BQU, CTQ2012-32436, Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT-420000-ACT1) and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637

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confidence: 99%

Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

et al. 2014

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“…32) [61], Li and coworkers developed a robust aminofluorination of alkenes catalyzed by silver (Fig. 37) [65]. A radical clock substrate underwent rearrangement, which supports the intermediacy of an alkyl radical.…”

Section: Fluorofunctionalization Of Alkenesmentioning

confidence: 96%

Transition Metal-Mediated and Metal-Catalyzed Carbon–Fluorine Bond Formation

Campbell

Hoover

Ritter

2014

Topics in Organometallic Chemistry

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The development of new C-F bond forming reactions from organotransition metal complexes has played a key role in advancing the field of fluorination chemistry and has allowed for improved access to fluorinated organic molecules of interest in medicine, materials, and agrochemicals. In this review, we describe the development of transition metal-mediated and metal-catalyzed fluorination methods over the past decade. Special attention is paid to the variety of organometallic mechanisms by which C-F bond formation can occur and the strengths and limitations of different approaches.

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“…[5,7] Addition of A across aC =Cbond in 1a affords the new alkyl radical intermediate B,w hich is also supported by the formation of the side-products 4a-c (entry 1i nT able 1). Oxidation of B by the active Ag II species generates the cation intermediate C, [3,7] followed by electrophilic alkylation of 3a …”

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confidence: 88%

Silver‐Mediated Intermolecular 1,2‐Alkylarylation of Styrenes with α‐Carbonyl Alkyl Bromides and Indoles

et al. 2016

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A new iron-facilitated silver-mediated radical 1,2-alkylarylation of styrenes with α-carbonyl alkyl bromides and indoles is described, and two new C-C bonds were generated in a single step through a sequence of intermolecular C(sp(3)-Br functionalization and C(sp(2))-H functionalization across the alkenes. This method provides an efficient access to alkylated indoles with broad substrate scope and excellent selectivity.

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Silver-Catalyzed Radical Aminofluorination of Unactivated Alkenes in Aqueous Media

Cited by 321 publications

References 67 publications

Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

Transition Metal-Mediated and Metal-Catalyzed Carbon–Fluorine Bond Formation

Silver‐Mediated Intermolecular 1,2‐Alkylarylation of Styrenes with α‐Carbonyl Alkyl Bromides and Indoles

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