Unbiased C3‐Electrophilic Indoles: Triflic Acid Mediated C3‐Regioselective Hydroarylation of N−H Indoles** DOI Creative Commons
Nazarii Sabat, Weiping Zhou, Vincent Gandon

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(30)

Published: May 16, 2022

Abstract The direct dearomative addition of arenes to the C3 position unprotected indoles is reported under operationally simple conditions, using triflic acid at room temperature. present regioselective hydroarylation a straightforward manner generate an electrophilic indole from unbiased in sharp contrast previous strategies. This atom‐economical method delivers biologically relevant 3‐arylindolines and 3,3‐spiroindolines high yields regioselectivities both intra‐ intermolecular processes. DFT computations suggest stabilization cationic or dicationic intermediates with H‐bonded (TfOH) n clusters.

Language: Английский

Csp2–H functionalization of phenols: an effective access route to valuable materials via Csp2–C bond formation DOI Creative Commons

Giulia Brufani,

Benedetta Di Erasmo,

Chao‐Jun Li

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(11), P. 3831 - 3871

Published: Jan. 1, 2024

In the vast majority of top-selling pharmaceutical and industrial products, phenolic structural motifs are highly prevalent. Non-functionalized simple phenols serve as building blocks in synthesis value-added chemicals. It is worth mentioning that lignin, being largest renewable biomass source aromatic nature, mainly consists units, which enable production structurally diverse phenols. Given their remarkable applicability chemical value chain, many efforts have been devoted to increasing molecular complexity scaffold. Among key techniques, direct functionalization Csp

Language: Английский

Citations

6
On-Water Accelerated Sulfenylation of Indole Derivatives under Visible Light Irradiation DOI Creative Commons

Jun Sup Lee,

Chulyong Lee,

Jiwon Jang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A visible-light promoted sulfenylation of N -carboxyindoles with thiols showed substantially higher rate and selectivity when conducted “on water”.

Language: Английский

Citations

0
Unbiased C3‐Electrophilic Indoles: Triflic Acid Mediated C3‐Regioselective Hydroarylation of N−H Indoles** DOI Creative Commons
Nazarii Sabat, Weiping Zhou, Vincent Gandon

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(30)

Published: May 16, 2022

The direct dearomative addition of arenes to the C3 position unprotected indoles is reported under operationally simple conditions, using triflic acid at room temperature. present regioselective hydroarylation a straightforward manner generate an electrophilic indole from unbiased in sharp contrast previous strategies. This atom-economical method delivers biologically relevant 3-arylindolines and 3,3-spiroindolines high yields regioselectivities both intra- intermolecular processes. DFT computations suggest stabilization cationic or dicationic intermediates with H-bonded (TfOH)

Language: Английский

Citations

10
One-Pot Synthesis of Core Structure of Shewanelline C Using an Azidoindoline DOI
Toshiki Yamashiro, Keisuke Tokushige, Takumi Abe

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(6), P. 3992 - 3997

Published: March 8, 2023

The unprecedented synthesis of the indolines bearing N3-quinazolin-2,4-dione moiety using an AZIN is reported. concise features tandem Staudinger/chemo-selective aza-Wittig/cyclization sequence AZINs with isatoic anhydride by a one-pot protocol.

Language: Английский

Citations

4
Mechanistic duality of indolyl 1,3-heteroatom transposition DOI Creative Commons
Yujin Lee,

Yun Seung Nam,

Soo Young Kim

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(28), P. 7688 - 7698

Published: Jan. 1, 2023

A novel mechanistic duality has been revealed from the indolyl 1,3-heteroatom transposition (IHT) of N-hydroxyindole derivatives. series in-depth investigations suggests that two separate mechanisms are operating simultaneously. Moreover, relative contribution each pathway, energy barrier for and identity primary pathway were shown to be functions electronic properties substrate system. Based on understanding obtained, a mechanism-driven strategy general efficient introduction heteroatom at 3-position indole developed. The reaction developed exhibits broad scope provide products in various forms functionalised indole. method is applicable both oxygen- nitrogen-based functional groups.

Language: Английский

Citations

4
Cu(I)-Catalyzed Atropselective Heterobiaryl Coupling Employing Umpoled Indoles DOI
Nguyen H. Nguyen,

Sanghyup Seo,

Jiwon Jang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(34), P. 7149 - 7154

Published: Aug. 20, 2024

An enantioselective Cu(I)-catalyzed coupling of N-carboxyindoles with various 2-naphthols and phenols for the synthesis axially chiral arylindoles has been developed. Our mechanistic studies, bolstered by experimental evidence DFT calculations, reveal a novel closed-shell mechanism involving outer-sphere attack on Cu-bound naphthols. This allows unprecedented diversity in C-H arylation. Enantiocontrol is achieved through center-to-axis chirality transfer via key dearomatized naphthol intermediate, which prevents undesired epimerization C-C axis.

Language: Английский

Citations

1
On the Barton Copper‐Catalyzed C3‐Arylation of Indoles using Triarylbismuth bis(trifluoroacetate) Reagents DOI Creative Commons

Ahmed Fnaiche,

Bianca Bueno,

Claire L. McMullin

et al.

ChemPlusChem, Journal Year: 2023, Volume and Issue: 88(8)

Published: Feb. 27, 2023

We disclose herein our detailed investigation into the Barton copper-promoted C3-arylation of indoles using triarylbismuth bis(trifluoroacetates). The arylation unsubstituted 1H-indole Barton's conditions gave a low yield C3-arylated indole, along with small amounts product double C2/C3-arylation and traces C2 arylation. On contrary, blocked at position is highly efficient, affording desired products in good to excellent yields. reaction operates under simple conditions, shows substrate scope, functional group compatibility, allows transfer electron-neutral or deficient aryl groups. Computational studies propose mechanism involving trifluoroacetate-assisted C-H activation step.

Language: Английский

Citations

3
C–H heteroarylation of aromatics via catalyst free SN2′ coupling cycloaromatization DOI

Qixing Lu,

Tao Wang, Qian Wu

et al.

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(11), P. 4399 - 4404

Published: Jan. 1, 2022

We have developed C–H heteroarylation of aromatics via a catalyst free S N 2′ coupling heterocycloaromatization that could realize the late-stage modification various marketed pharmaceuticals or functional materials.

Language: Английский

Citations

4
Nucleophilic C4-selective (hetero) arylation of pyridines for facile synthesis of heterobiaryls DOI Creative Commons
Kewon Kim, Euna You, Sungwoo Hong

et al.

Frontiers in Chemistry, Journal Year: 2023, Volume and Issue: 11

Published: Sept. 1, 2023

The synthesis of heterobiaryl compounds holds significant value in organic chemistry due to their extensive range applications. Herein, we report a highly efficient strategy for conducting C4-selective (hetero) arylation pyridines using N -aminopyridinium salts. reaction proceeds readily at room temperature the presence base, thus eliminating requirement catalysts or oxidants. This method allows installation various electron-rich aryl groups on pyridines, resulting streamlined valuable C4-(hetero) pyridine derivatives, which are otherwise challenging acquire via conventional methods. simple and straightforward will facilitate access thereby promoting application scientific disciplines.

Language: Английский

Citations

1
Unbiased C3‐Electrophilic Indoles: Triflic Acid Mediated C3‐Regioselective Hydroarylation of N−H Indoles** DOI Creative Commons
Nazarii Sabat, Weiping Zhou, Vincent Gandon

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(30)

Published: May 16, 2022

Abstract The direct dearomative addition of arenes to the C3 position unprotected indoles is reported under operationally simple conditions, using triflic acid at room temperature. present regioselective hydroarylation a straightforward manner generate an electrophilic indole from unbiased in sharp contrast previous strategies. This atom‐economical method delivers biologically relevant 3‐arylindolines and 3,3‐spiroindolines high yields regioselectivities both intra‐ intermolecular processes. DFT computations suggest stabilization cationic or dicationic intermediates with H‐bonded (TfOH) n clusters.

Language: Английский

Citations

1