Regio- and Stereoselective β-Sulfonylamination of Alkynes via Photosensitized Bifunctional N–S Bond Homolysis DOI

Tonglv Pu,

Si‐Hai Wu,

Liuyan Cai

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 4, 2024

Nitrogen central radicals (NCRs) are versatile synthetic intermediates for creating functional nitrogen-containing molecules. Herein, a photosensitized β-sulfonylamination of terminal alkynes as well acetylene has been established by employing N-sulfonyl heteroaromatics bifunctional reagents (BFRs) to efficiently deliver (E)-β-sulfonylvinylamines with excellent regio- and stereoselectivities. Mechanistic studies suggest base-accelerated energy transfer (EnT) photocatalysis involving aromatic NCR formation, radical addition alkynes, sulfonylation processes.

Language: Английский

Photoredox-Catalyzed Alkene Acylesterification with Acyloxime Esters via C–C and Tertiary C–O Bond Formation DOI

Youkang Zhou,

Ruiying Zhao, Mingyou Hu

et al.

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

Published: Jan. 7, 2025

We describe an efficient acyl esterification method for alkenes utilizing acyloxime esters as bifunctional reagents featuring radical acylation and congested C–O bond formation. This approach is characterized by mild photoredox conditions, high step atom economy, a broad substrate scope, excellent regioselectivity. A variety of valuable α-acyl hindered alcohol esters, including those obtained via gram-scale synthesis late-stage functionalization pharmaceutical molecules, were presented, demonstrating its synthetic potential practicability.

Language: Английский

Citations

3
Visible-Light-Induced Redox-Neutral Difunctionalization of Alkenes and Alkynes DOI
Susmita Mondal, Sumit Ghosh, Alakananda Hajra

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(72), P. 9659 - 9691

Published: Jan. 1, 2024

The twelve principles of green chemistry illuminate the pathway in direction sustainable and eco-friendly synthesis, marking a fundamental shift synthetic organic paradigms. In this realm, harnessing power visible light for difunctionalization various skeletons without employing any external oxidant or reductant, specifically termed as redox-neutral difunctionalization, has attracted tremendous interest from chemists due to its low cost, easy availability environmentally friendly nature contrast traditional metal-catalyzed difunctionalizations. This review presents an overview recent updates on visible-light-induced reactions with literature coverage up May 2024.

Language: Английский

Citations

12
Catalyst-Free Selective Synthesis of E-Tetrasubstituted Olefins via Tandem Reaction of 3-Acetyl-4-phenyl-1-oxaspiro[4.5]deca-3,6,9-triene-2,8-dione with Amine, C–C Bond Breakage, and Proton Transfer DOI
Tingting Zhang, Xinkun An,

Guoen Cui

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

The Z- or E-selective syntheses of tetrasubstituted olefins present big challenges. Tremendous efforts are ongoing to overcome this issue, especially for acyclic structures. In work, an E-stereoselective synthetic method through tandem reaction 1,4-Michael addition 3-acetyl-4-phenyl-1-oxaspiro[4.5]deca-3,6,9-triene-2,8-dione with amine, C-C bond breakage, and proton transfer by intermolecular hydrogen bonds was revealed excellent atom economy without catalysts additives. A diverse set E-tetrasubstituted were obtained in 43% 93% yields functional group tolerance late-stage modifications complex drug molecules. mechanism proposed based on the deuterium-labeling experiment density theory (DFT) calculation.

Language: Английский

Citations

1
Energy Transfer (EnT)-Mediated Stereoselective Aryl-Heterofunctionalization of Unactivated Alkynes via Radical Rearrangement DOI

Xin-Chao Meng,

Tai‐Long Pan,

Feng Yang

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 5, 2025

In this study, we present a novel catalyst-free energy transfer mediated radical rearrangement strategy for the aryl-heterofunctionalization of unactivated alkynes, leading to synthesis polyfunctional olefins with exceptional stereoselectivity. This innovative approach, driven by visible light, exemplifies green chemistry principles eliminating reliance on transition metals, external oxidants, and photocatalysts. The broad applicability our method is demonstrated through successful diverse array compounds, including vinyl sulfones, selenides, sulfides. Preliminary mechanistic insights suggest an mechanism, highlighting efficiency selectivity strategy.

Language: Английский

Citations

0
Photoinduced Carbamoylarylation of Alkynes with N-Aryl Oxamic Acids DOI
Kohei Sekine,

Gaofan Yue,

Joji Kajiwara

et al.

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

Published: April 2, 2025

1,2-Difunctionalization of alkynes is an attractive synthetic protocol, because it can achieve a high step economy and provide various complex organic molecules. This study demonstrates the visible-light-induced carbamoylarylation terminal using N-aryl oxamic acids as bifunctional reagents. The transformation involves addition carbamoyl radicals to alkenes, resulting in 1,4-aryl migration via C(aryl)-N bond cleavage afford corresponding arylacrylamides moderate good yields.

Language: Английский

Citations

0
Z-selective radical difunctionalization of aromatic alkynes: synthesis of multi-substituted triarylethenes DOI

Xinxin Wang,

Jie Wang,

Meishan Ji

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(37), P. 4894 - 4897

Published: Jan. 1, 2024

Described herein is a Cu-catalyzed diarylation of aromatic alkynes via radical docking-migration pathways, leading to broad range valuable triarylethenes.

Language: Английский

Citations

3
Photoredox Catalyzed Conia-Ene-Type Cyclization/Smiles Rearrangement Cascade Reactions to Access Substituted Methylenecarbocycles DOI

Keyuan Zhang,

Qi Jiang,

Chonglong He

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(37), P. 7971 - 7975

Published: Sept. 11, 2024

We report a novel visible-light-driven photoredox-catalyzed cascade reaction involving Conia-ene-type cyclization and Smiles rearrangement initiated from alkyne-tethered α-sulfonyl esters. This methodology not only facilitates the rapid synthesis of broad spectrum highly substituted methylenecarbocycles but also introduces new mechanistic pathway with aryl group migration, surpassing conventional 1,5-hydrogen shift typically observed in Conia-ene reactions.

Language: Английский

Citations

3
Alkylarylation of alkenes with arylsulfonylacetate as bifunctional reagent via photoredox radical addition/smiles rearrangement cascade DOI

Chonglong He,

Yulong Wang, Quanxin Li

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110253 - 110253

Published: July 1, 2024

Language: Английский

Citations

2
Regio- and Stereoselective β-Sulfonylamination of Alkynes via Photosensitized Bifunctional N–S Bond Homolysis DOI

Tonglv Pu,

Si‐Hai Wu,

Liuyan Cai

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 4, 2024

Nitrogen central radicals (NCRs) are versatile synthetic intermediates for creating functional nitrogen-containing molecules. Herein, a photosensitized β-sulfonylamination of terminal alkynes as well acetylene has been established by employing N-sulfonyl heteroaromatics bifunctional reagents (BFRs) to efficiently deliver (E)-β-sulfonylvinylamines with excellent regio- and stereoselectivities. Mechanistic studies suggest base-accelerated energy transfer (EnT) photocatalysis involving aromatic NCR formation, radical addition alkynes, sulfonylation processes.

Language: Английский

Citations

1