Efficient C–H/C–N and C–H/C–CO–N Conversion via Decatungstate-Photoinduced Alkylation of Diisopropyl Azodicarboxylate

Ryu, Ilhyong; Tani, Akihiro; Fukuyama, Takahide; Ravelli, Davide; Montanaro, Sara; Fagnoni, Maurizio

doi:10.1021/ol401061v

Cited by 152 publications

(110 citation statements)

References 52 publications

(27 reference statements)

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“…The process is efficient with electron-poor olefins such as 102, but not with simple alkenes and vinyl ethers, again emphasizing the role of polar effects in such reactions. Other acceptors such as dialkyl azodicarboxylates may enter into a similar cascade process, as shown by the reaction involving cyclohexane 104, CO, and DIAD 105, affording acylhydrazine 106 in good yield (2) [70]. Unimolecular chain transfer reagent ethynyl triflone 108 is known to afford, upon addition-elimination, the trifluoromethyl radical that can abstract hydrogens from alkanes.…”

Section: Alkane Carbonylationmentioning

confidence: 99%

Free‐Radical Multicomponent Processes

Liautard

Landais

2014

Multicomponent Reactions in Organic Synthesis

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Section: Alkane Carbonylationmentioning

confidence: 99%

Free‐Radical Multicomponent Processes

Liautard

Landais

2014

Multicomponent Reactions in Organic Synthesis

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“… a) Proposed mechanism for a polyoxotungstate complex acting as an H atom transfer catalyst. b) Three synthetic applications …”

Section: Radical–metal Crossover Reactionsmentioning

confidence: 99%

The Persistent Radical Effect in Organic Synthesis

2019

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Radical–radical couplings are mostly nearly diffusion‐controlled processes. Therefore, the selective cross‐coupling of two different radicals is challenging and not a synthetically valuable transformation. However, if the radicals have different lifetimes and if they are generated at equal rates, cross‐coupling will become the dominant process. This high cross‐selectivity is based on a kinetic phenomenon called the persistent radical effect (PRE). In this Review, an explanation of the PRE supported by simulations of simple model systems is provided. Radical stabilities are discussed within the context of their lifetimes, and various examples of PRE‐mediated radical–radical couplings in synthesis are summarized. It is shown that the PRE is not restricted to the coupling of a persistent with a transient radical. If one coupling partner is longer‐lived than the other transient radical, the PRE operates and high cross‐selectivity is achieved. This important point expands the scope of PRE‐mediated radical chemistry. The Review is divided into two parts, namely 1) the coupling of persistent or longer‐lived organic radicals and 2) “radical–metal crossover reactions”; here, metal‐centered radical species and more generally longer‐lived transition‐metal complexes that are able to react with radicals are discussed—a field that has flourished recently.

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“…This strategy allowed for the construction of numerous C−C,15 C−Si,16 C−N,17 and C−F18 bonds 15a, 19. Intrigued by these seminal reports, we wondered if DT catalysis could be used to effect selective C(sp 3 )−H aerobic oxidation.…”

mentioning

confidence: 99%

Selective C(sp³)−H Aerobic Oxidation Enabled by Decatungstate Photocatalysis in Flow

et al. 2018

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A mild and selective C(sp3)−H aerobic oxidation enabled by decatungstate photocatalysis has been developed. The reaction can be significantly improved in a microflow reactor enabling the safe use of oxygen and enhanced irradiation of the reaction mixture. Our method allows for the oxidation of both activated and unactivated C−H bonds (30 examples). The ability to selectively oxidize natural scaffolds, such as (−)‐ambroxide, pregnenolone acetate, (+)‐sclareolide, and artemisinin, exemplifies the utility of this new method.

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Efficient C–H/C–N and C–H/C–CO–N Conversion via Decatungstate-Photoinduced Alkylation of Diisopropyl Azodicarboxylate

Cited by 152 publications

References 52 publications

Free‐Radical Multicomponent Processes

Free‐Radical Multicomponent Processes

The Persistent Radical Effect in Organic Synthesis

Selective C(sp³)−H Aerobic Oxidation Enabled by Decatungstate Photocatalysis in Flow

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Efficient C–H/C–N and C–H/C–CO–N Conversion via Decatungstate-Photoinduced Alkylation of Diisopropyl Azodicarboxylate

Cited by 152 publications

References 52 publications

Free‐Radical Multicomponent Processes

Free‐Radical Multicomponent Processes

The Persistent Radical Effect in Organic Synthesis

Selective C(sp3)−H Aerobic Oxidation Enabled by Decatungstate Photocatalysis in Flow

Contact Info

Product

Resources

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Selective C(sp³)−H Aerobic Oxidation Enabled by Decatungstate Photocatalysis in Flow