Recent advances of aminoazanium salts as amination reagents in organic synthesis

Xu, Jianeng; Du, Cuiwei; Liu, Chao

doi:10.1039/d2ob01312f

Cited by 6 publications

(3 citation statements)

References 69 publications

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“…The synthetic potential of N-aminopyridinium salts as versatile nitrogen radical surrogates has been demonstrated in various transformations including cycloaddition and difunctionalization reactions of alkenes and alkynes. 36,37,38 However, application of these salts for the reaction with BCBs may pose considerable challenges due to the highly reactive nature of BCBs, raising concerns about regio-and chemoselectivity issues, and therefore, leading to undesired reaction pathways.…”

Section: Reaction Developmentmentioning

confidence: 99%

Photoredox-Catalyzed Amidyl Radical Insertion to Bicyclo[1.1.0]butanes

Glorius,

Chintawar,

Laskar

et al. 2024

Preprint

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Heteroaromatic rings play a prominent role in medicinal chemistry, featuring in numerous biologically relevant molecules. However, unlike benzene ring the saturated and structurally rigid bioisosteric mimetics of heteroaromatic rings are rarely known, mainly due to the inherent challenges associated with the stability and synthesis of heteroatom-substituted C(sp3)-rich polycyclic hydrocarbons. We envisioned that the strategic and highly selective insertion of different heteroatomic units to bicyclo[1.1.0]butanes (BCBs) could offer an ideal platform to access diverse heterobicyclo[n.1.1]alkanes. Herein, by circumventing the intrinsic challenges associated with the reaction of BCBs with heteroatomic radicals, we report a photoredox-catalyzed highly regio- and chemoselective insertion of amidyl radicals to BCBs, which provided direct access to 2-oxa-4-azabicyclo[3.1.1]hept-3-enes. Detailed experimental and computational studies have been carried out to underpin the mechanistic paradigm of this reaction. The newly synthesized heterobicyclic motifs are structurally rigid and exhibit well-defined exit vectors, the two important molecular properties in medicinal chemistry. Moreover, various downstream transformations were carried out with these compounds, highlighting their utility as versatile building blocks in synthetic chemistry.

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Section: Reaction Developmentmentioning

confidence: 99%

Photoredox-Catalyzed Amidyl Radical Insertion to Bicyclo[1.1.0]butanes

Glorius,

Chintawar,

Laskar

et al. 2024

Preprint

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“…Following a similar activation model ( Figure 2 ), several addition sequences of radical species to N- alkoxy and N -amine azaarenium platform molecules (R 1 = OR, NR 2 ) emerged in the literature as powerful functionalization strategies showing that the regioselectivity issue highly depends on the architecture and substitution pattern of the heterocycles. This field of research was covered by very instructive recent reviews [ 17 , 18 , 19 , 20 , 21 ].…”

Section: Introductionmentioning

confidence: 99%

“…In this review, we intend to cover the recent evolution of the catalytic and technology-driven addition of radical species to iminium and azaarenium compounds having a trisubstituted nitrogen atom ( Figure 2 , R 1 ≠ H). In a complementary point of view of what has been covered in the literature, we will hereby focus on both dipole derivatives (N-R 1 with R 1 = Y − ) and N -alkyl azaarenium salt, which has never been covered in a unified fashion despite some sporadic examples being found in previous reviews on pyridine derivatives [ 17 , 18 , 19 , 20 , 21 , 22 , 23 ]. We essentially cover the literature from 2015, since the Opatz’s review has already discussed this field of research before [ 14 ].…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Catalytic and Technology-Driven Radical Addition to N,N-Disubstituted Iminium Species

et al. 2023

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Recently, radical chemistry has grown exponentially in the toolbox of organic synthetic chemists. Upon the (re)introduction of modern catalytic and technology-driven strategies, the implementation of highly reactive radical species is currently facilitated while expanding the scope of numerous synthetic methodologies. In this context, this review intends to cover the recent advances in radical-based transformations of N,N-disubstituted iminium substrates that encompass unique reactivities with respect to imines or protonated iminium salts. In particular, we have focused on the literature concerning the dipole type substrates, such as nitrones or azomethine imines, together with the chemistry of N+-X− (X = O, NR) azaarenium dipoles, which proved to be very versatile platforms in that field of research. The N-alkylazaarenium salts were been considered, which demonstrated specific reactivity profiles in radical chemistry.

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Photoredox Radical Cascade Cyclization of 2‐Alkynylarylnitriles in Visible Light: Direct Access to 3‐Amino‐1‐indenones

Rajput,

Garg,

Jain

2024

Adv Synth Catal

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A photoinduced direct synthesis of 3‐amino‐1‐indenones via radical cascade cyclization strategy is demonstrated. The methodology involves a domino reaction between 2‐alkynylarylnitrile and N‐aminopyridinium salt and captures the reactivity of in‐situ generated nitrogen‐centered radical (NCR) in visible light. Multiple bond‐forming events including C‐N, C‐C, and C‐O take place sequentially on 2‐alkynylarylnitrile enabling construction of 3‐amino‐1‐indenone core at room temperature in 35‐76% yields. A preliminary biological screening of synthesized compounds is indicative of their potent anti‐cancer property.

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Recent advances of aminoazanium salts as amination reagents in organic synthesis

Abstract: Nitrogen-containing organic compounds are widely distributed in natural products, pharmaceuticals, and functional materials. Several methods have been reported to construct C-N bond including Curtius rearrangement, Schmidt rearrangement, Ullmann reaction, etc....

Cited by 6 publications

References 69 publications

Photoredox-Catalyzed Amidyl Radical Insertion to Bicyclo[1.1.0]butanes

Photoredox-Catalyzed Amidyl Radical Insertion to Bicyclo[1.1.0]butanes

Recent Advances in Catalytic and Technology-Driven Radical Addition to N,N-Disubstituted Iminium Species

Photoredox Radical Cascade Cyclization of 2‐Alkynylarylnitriles in Visible Light: Direct Access to 3‐Amino‐1‐indenones

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