XAT‐Catalysis for Intramolecular Biaryl Synthesis DOI Creative Commons
Thomas Sephton,

Jonathan M. Large,

Louise S. Natrajan

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(35)

Published: May 31, 2024

Abstract Radical ipso‐ substitution offers an alternative to organometallic approaches for biaryl synthesis, but usually requires stoichiometric reagents such as tributyltin hydride. Here, we demonstrate that visible light photoredox catalysis can be used ipso ‐biaryl via a halogen‐atom transfer (XAT) regime. Using amide substrates promote over unwanted ortho‐ addition, smooth formation with no constraint on the electronic character of migrating arene ring. The photoreaction combined in one operation achieve formal arylation inert aniline C−N bond.

Language: Английский

XAT‐Catalysis for Intramolecular Biaryl Synthesis DOI Creative Commons
Thomas Sephton,

Jonathan M. Large,

Louise S. Natrajan

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(35)

Published: May 31, 2024

Radical ipso-substitution offers an alternative to organometallic approaches for biaryl synthesis, but usually requires stoichiometric reagents such as tributyltin hydride. Here, we demonstrate that visible light photoredox catalysis can be used ipso-biaryl via a halogen-atom transfer (XAT) regime. Using amide substrates promote ipso- over unwanted ortho-addition, smooth formation with no constraint on the electronic character of migrating arene ring. The photoreaction combined in one operation achieve formal arylation inert aniline C-N bond.

Language: Английский

Citations

5

Aryne‐Enabled C−N Arylation of Anilines DOI Creative Commons
Thomas Sephton, Anastasios Charitou, Cristina Trujillo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Oct. 18, 2023

Abstract Anilines are potentially high‐value arylating agents, but limited by the low reactivity of strong C−N bond. We show that reactive intermediate benzyne can be used to both activate anilines, and set‐up an aryl transfer reaction in a single step. The does not require any transition metal catalysts or stoichiometric organometallics, establishes metal‐free route valuable biaryl products functionalizing aniline

Language: Английский

Citations

11

Cascade Aryne Aminoarylation for Biaryl Phenol Synthesis DOI Creative Commons
A.K. Das,

Danielle L. Myers,

Venkataraman Ganesh

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(13), P. 2612 - 2616

Published: March 21, 2024

We describe a transition metal-free approach to hindered 3-amino-2-aryl phenols through cascade nucleophilic addition / Smiles–Truce rearrangement of functionalized Kobayashi aryne precursor. Under anionic conditions, secondary alkyl amines add the intermediate set up an aryl transfer from neighboring sulfonate group. The use sulfonate, rather than more typical sulfonamide, enables access phenolic biaryl products that are important motifs in natural and pharmaceuticals.

Language: Английский

Citations

3

Rhodium‐Catalyzed Direct ortho‐Arylation of Anilines DOI
Clément Jacob, Julien Annibaletto,

Ju Peng

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: April 29, 2024

Abstract An efficient and broadly applicable rhodium‐catalyzed direct ortho ‐arylation of anilines with aryl iodides relying on readily available aminophosphines as traceless directing groups is reported. Its scope functional group compatibility were both found to be quite broad a large variety (hetero)aryl iodides, including complex ones, could utilized. The ‐arylated obtained in high average yields, without any competing diarylation full regioselectivity, which constitutes major step forward compared other processes. reaction moreover not limited an bromide triflate successfully used, extended diarylation. Mechanistic studies revealed the key unique role aminophosphine, acting only substrate but also ligand for rhodium catalyst.

Language: Английский

Citations

3

Precise synthesis of ortho-deuterated aromatic derivatives: an arylthianthrenium salt-based platform approach DOI

Yunhao Guan,

Peng Xia, Rong Fan

et al.

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111132 - 111132

Published: March 1, 2025

Language: Английский

Citations

0

Gold/Copper Dual-Catalyzed Annulation of Arynes with Phosphites: A Synthetic Strategy for Dibenzophospholes DOI
Donghwa Shin, Seo‐Jung Han

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 27, 2025

A synthetic approach to dibenzophospholes was developed via the gold- and copper-catalyzed annulation reactions of arynes phosphites. The reaction conditions demonstrated a broad functional group tolerance, enabling synthesis diverse range dibenzophosphole 5-oxides. This method is useful for preparing with unique optical electronic properties.

Language: Английский

Citations

0

Aryne Polymerization Enabled by Pyrazole-Induced Nucleophilic Aromatic Substitution DOI
Hayato Fujimoto,

Shisato Yamamura,

Mamoru Tobisu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 14, 2025

Despite the widespread use of arynes in organic synthesis, their polymerization remains a significant challenge due to intrinsic instability and short lifetime aryne intermediates. Here, we report method for using simple organonucleophile, N-arylpyrazole, as an initiator. This proceeds via unique pyrazole-induced nucleophilic aromatic substitution mechanism, facilitating formation poly(ortho-arylene)s with narrow polydispersity well-defined structures. The high chemical stability N-arylpyrazole allows broader scope applications, including at side chain preformed polymers (graft polymerization) synthesis star-shaped poly(ortho-arylene)s.

Language: Английский

Citations

0

Aryne-Activated Smiles Rearrangement of Anilines DOI
Dahui Zhao,

Xiaohan Wan

Synfacts, Journal Year: 2024, Volume and Issue: 20(03), P. 0246 - 0246

Published: Feb. 14, 2024

Key words metal-free protocol - arynes aniline biaryl synthesis C–N arylation Smiles–Truce rearrangement

Language: Английский

Citations

0

Rhodium‐Catalyzed Direct ortho‐Arylation of Anilines DOI
Clément Jacob, Julien Annibaletto,

Ju Peng

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(30)

Published: April 29, 2024

Abstract An efficient and broadly applicable rhodium‐catalyzed direct ortho ‐arylation of anilines with aryl iodides relying on readily available aminophosphines as traceless directing groups is reported. Its scope functional group compatibility were both found to be quite broad a large variety (hetero)aryl iodides, including complex ones, could utilized. The ‐arylated obtained in high average yields, without any competing diarylation full regioselectivity, which constitutes major step forward compared other processes. reaction moreover not limited an bromide triflate successfully used, extended diarylation. Mechanistic studies revealed the key unique role aminophosphine, acting only substrate but also ligand for rhodium catalyst.

Language: Английский

Citations

0

Aminoarylation of Alkynes using Diarylanilines DOI Creative Commons

Zi Liu,

Michael F. Greaney

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(49), P. 6296 - 6299

Published: Jan. 1, 2024

Intermolecular aminoarylation of alkynes is described,

Language: Английский

Citations

0