Isolation and Characterization of Sulfonium-Ylide-Stabilized Palladium Carbenes DOI
Martin Stang, Suzanne A. Blum

Organometallics, Journal Year: 2024, Volume and Issue: 44(1), P. 169 - 178

Published: Dec. 17, 2024

Isolable sulfonium-ylide-stabilized palladium carbene complexes were synthesized through palladium(II)-induced cyclization of 1,2-alkynylarylsulfanes. X-ray crystallographic analysis characterized the maintenance a +2 oxidation state, with carbene-carbon–palladium bond lengths 1.95 Å, indicating partial double-bond character. These endocyclic sulfonium ylide carbenes represent first and/or isolable examples this ligand class; such groups previously proposed as reaction intermediates during cyclization–carbonylation reactions. A variety palladium(II) bearing sulfonium-ylide ligands, differing substituents, synthesized, and structure stability these in solution analyzed by 1H 13C NMR spectroscopy, revealing reversibility dependence on substituents. The chirality sulfur heteroatom overall properties ligands provide potential electronic steric alternative to existing which could facilitate future development complementary metal-based reactivity.

Language: Английский

EDA Complex-Enabled Annulation to Access CF2-Containing Tetralones and Quinazolinones Using Persulfates as Electron Donors DOI
Shupeng Zhang, Dawei Guo,

Mei-Ling Yang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(15), P. 10614 - 10623

Published: July 25, 2024

A photocatalyst-free and EDA complex-enabled radical cascade cyclization reaction of inactive alkenes with bromodifluoroacetamides was reported for the divergent synthesis fluorine-containing tetralones quinazolinones. In this transformation, persulfates as electron donors difluoro bromamide acceptors generate complex. This is a promising photochemical method advantages such mild conditions, simple operation, being metal-free, excellent functional group tolerance.

Language: Английский

Citations

6
Sustainable Synthesis through Catalyst‐Free Photoinduced Cascaded Bond Formation DOI
Rosalin Bhanja, Shyamal Kanti Bera, Prasenjit Mal

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: 19(14)

Published: May 8, 2024

The beginning of photochemical reactions revolutionized synthetic chemistry through sustainable practices. This review explores cutting-edge developments in leveraging light-induced processes for generating cascaded C-C and C-hetero bonds without catalysts. Significantly, catalyst-free photoinduced methodologies have garnered considerable attention, especially the creation varied heterocyclic frameworks drug design synthesis natural products. article delves into underlying mechanisms, addresses limitations, evaluates various methodologies, emphasizing potential photocatalyst transition metal-free to enhance sustainability. Divided two sections, it covers recent strides C-heteroatom multiple bond formation reactions.

Language: Английский

Citations

4
Synthesis of Acylbenzo[b]thiophenes, Benzofurans and Indoles via Intramolecular Oxidative Cyclization Enabled by Photocatalytic Hydrogen Atom Transfer (HAT) DOI Creative Commons

Fen-Dou Wang,

Jin Jiang,

Tiantian Xu

et al.

Tetrahedron Chem, Journal Year: 2025, Volume and Issue: unknown, P. 100119 - 100119

Published: Jan. 1, 2025

An efficient strategy for intramolecular oxidative cyclization of 2-alkynylthioanisoles toward 3-acylbenzo[b]thiophenes by photochemical hydrogen atom transfer catalysis has been developed. 3-Acylbenzo[b]selenophenes, benzofurans and indoles can also be prepared this protocol. This reaction is convenient to perform at room temperature under simple conditions using air as the oxidant. Mechanistic studies revealed that formation α-thioalkyl radicals intermediate crucial.Graphical abstract

Language: Английский

Citations

0
Synthesis and Biological Evaluation of Thiophene and Its Derivatives DOI
Binoyargha Dam, Bhisma K. Patel

Published: Jan. 1, 2024

Language: Английский

Citations

0
Developments in the Construction of Benzo[b]thiophenes from 2‐Alkynylthioanisoles by Electrophilic and Radical Cyclization Reactions DOI

Tianbo Shang,

Chao Ma, Mengyu Xie

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 1, 2024

Abstract Benzo[ b ]thiophene moieties are important skeletons which have been widely found in many natural products, pharmaceuticals, as well functionalized materials. 2‐Alkynylthioanisoles, a class of bifunctional compounds bearing methylthio and alkynyl groups, easily accessible from Pd‐catalyzed Sonogashira coupling between 2‐halothioanisoles terminal alkynes, employed synthons the construction benzo[b]thiophenes through an electrophilic or radical pathway. This review summarizes related developments with particular focus on reaction mechanism. We hope it will help future research this area believe that discovery new catalytic systems, industrial synthesis benzo[ ]thiophenes 2‐alkynylthioanisoles be achieved soon.

Language: Английский

Citations

0
Isolation and Characterization of Sulfonium-Ylide-Stabilized Palladium Carbenes DOI
Martin Stang, Suzanne A. Blum

Organometallics, Journal Year: 2024, Volume and Issue: 44(1), P. 169 - 178

Published: Dec. 17, 2024

Isolable sulfonium-ylide-stabilized palladium carbene complexes were synthesized through palladium(II)-induced cyclization of 1,2-alkynylarylsulfanes. X-ray crystallographic analysis characterized the maintenance a +2 oxidation state, with carbene-carbon–palladium bond lengths 1.95 Å, indicating partial double-bond character. These endocyclic sulfonium ylide carbenes represent first and/or isolable examples this ligand class; such groups previously proposed as reaction intermediates during cyclization–carbonylation reactions. A variety palladium(II) bearing sulfonium-ylide ligands, differing substituents, synthesized, and structure stability these in solution analyzed by 1H 13C NMR spectroscopy, revealing reversibility dependence on substituents. The chirality sulfur heteroatom overall properties ligands provide potential electronic steric alternative to existing which could facilitate future development complementary metal-based reactivity.

Language: Английский

Citations

0