Palladium-Catalyzed Denitrogenative Cross-Coupling of Silicon-Masked, Aryl-Substituted Diazenes and Aryl Bromides

Finck, Lucie; Dabrowski, Sarah; Oestreich, Martin

doi:10.1055/a-1988-6052

Cited by 3 publications

(3 citation statements)

References 32 publications

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“…Following a minor reoptimization of the reaction parameters, 50 Organ's Pd-PEPPSI-i-Pr precatalyst 54 was found to effectively promote the targeted transformation in the presence of the base NaOt-Bu, thereby delivering a variety of functionalized biaryl compounds (as in 36ga−d) in moderate to good yields (11 + 31 → 36; Scheme 16). 55 Mechanistically, the extrusion of dinitrogen likely takes place in the aryl(diazenyl)palladium(II) complex 35 after the transmetalation step (see Scheme 15).…”

Section: Silicon-protected Diazenyl Anion Equivalentsmentioning

confidence: 99%

Bond-Forming Processes Enabled by Silicon-Masked Aryl- and Alkyl-Substituted Diazenes

Finck,

Oestreich

2023

J. Org. Chem.

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Aryl-and alkyldiimides (R−N�NH with R = aryl or alkyl) are elusive intermediates of valuable synthetic use, as they are assumed to be transient species in processes involving both carbon (with concomitant loss of N 2 ) and nitrogen nucleophiles (with conservation of the N�N moiety). The actual compounds are fragile and as such not bench stable which is why they have not yet found the attention they deserve. Conversely, early contributions showed that the stability of the parent diimide is significantly increased by replacing the hydrogen atom by a silyl group, but the synthetic applicability of these silicon-protected aryl-and alkyldiazenes has been far less explored, in part due to the absence of general procedures for their preparation. This Perspective provides an overview of the underexplored diazene chemistry that has witnessed considerable progress in recent years and highlights the potential of this motif in a range of synthetically useful (catalytic) transformations. The rediscovered siliconmasked diazenes constitute a versatile platform possessing enhanced stability and tamed reactivity in comparison to the parent hydrogen-substituted diimides. Aryl, diazenyl, and alkyl anionic key intermediates can be selectively generated in situ under Lewis base or transition metal catalysis, giving rise to novel synthetic approaches as viable alternatives to the already existing methodologies.

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Section: Silicon-protected Diazenyl Anion Equivalentsmentioning

confidence: 99%

Bond-Forming Processes Enabled by Silicon-Masked Aryl- and Alkyl-Substituted Diazenes

Finck,

Oestreich

2023

J. Org. Chem.

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“…Recently rediscovered and synthetically versatile N -aryl- N′ -silyldiazenes begin to find useful applications as latent aryl pronucleophiles. − Anionic Lewis bases mediate their desilylation, generating aryl-substituted diazenyl anions that eventually collapse into dinitrogen and aryl nucleophiles that can be decorated with a broad spectrum of functional groups. Accordingly, we have been seeking new reactions for these silicon-masked aryl pronucleophiles.…”

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confidence: 99%

Fluoride-Catalyzed Arylation of α-(Trifluoromethyl)styrene Derivatives with Silicon-Masked, Functionalized Aryl Pronucleophiles

Rahman

Oestreich

2023

Org. Lett.

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An operationally simple transition-metal-free protocol for the arylation of α-(trifluoromethyl)styrene derivatives with silicon-protected functionalized aryl pronucleophiles is disclosed. Catalytic amounts of an anionic Lewis base such as fluoride trigger the release of the aryl nucleophile from N-aryl-N′-silyldiazenes by desilylation along with denitrogenation. The thus-generated carbon nucleophiles engage in an allylic displacement with α-(trifluoromethyl)styrene electrophiles to afford the corresponding geminal difluoroalkenes.

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“…We recently rediscovered the use of N -aryl- N ′-silyldiazenes as latent aryl nucleophiles. − Anionic Lewis bases mediate their desilylation, formally generating an aryl-substituted diazenyl anion that eventually collapses into dinitrogen and the desired aryl nucleophile. For example, catalytic amounts of sodium trimethylsilanolate initiate an autocatalytic arylation of aldehydes .…”

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confidence: 99%

Synthesis of Benzhydryl-Substituted Amines by Silanolate-Mediated Aldimine Arylation with Functionalized Aryl Nucleophiles Released from Diazene-Based Reagents

et al. 2022

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A transition-metal-free protocol for the arylation of N-phenyl-and N-benzoyl-substituted, benzaldehyde-derived imine derivatives with functionalized aryl pronucleophiles is reported. The aryl nucleophiles are released from siliconprotected aryl-substituted diazenes by desilylation with potassium trimethylsilanolate concomitant with the loss of dinitrogen. A broad range of functional groups is tolerated in the aryl nucleophile but, depending upon their electronic effect, require specific groups at the imine nitrogen atom.

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Palladium-Catalyzed Denitrogenative Cross-Coupling of Silicon-Masked, Aryl-Substituted Diazenes and Aryl Bromides

Cited by 3 publications

References 32 publications

Bond-Forming Processes Enabled by Silicon-Masked Aryl- and Alkyl-Substituted Diazenes

Bond-Forming Processes Enabled by Silicon-Masked Aryl- and Alkyl-Substituted Diazenes

Fluoride-Catalyzed Arylation of α-(Trifluoromethyl)styrene Derivatives with Silicon-Masked, Functionalized Aryl Pronucleophiles

Synthesis of Benzhydryl-Substituted Amines by Silanolate-Mediated Aldimine Arylation with Functionalized Aryl Nucleophiles Released from Diazene-Based Reagents

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