Pyrimidinyl and pyrazinyl radicals were generated under moderate energetic irradiation conditions (UVA), and proved to be prompt to undergo C-C bond formation processes. Hetero-biaryl derivatives were obtained in good to high yields with highly interesting functional group selectivities. Bis hetero-biaryls were also easily accessible leading to original compounds, ready for further transformations. Experiments supporting radical processes have been reported.
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http://dx.doi.org/10.1039/c5cc08927a | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Cardiff University, School of Chemistry, Park Place, Main Building, CF10 3AT, Cardiff, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
Despite the remarkable advancements in hypervalent iodine chemistry, exploration of bromine and chlorine analogues remains in its infancy due to their difficult synthesis. Herein, we introduce six-membered cyclic λ3-bromanes and λ3-chloranes. Through single-crystal X-ray structural analyses and conformational studies, we delineate the crucial bonding patterns pivotal for the thermodynamic stability of these compounds.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
College of Pharmaceutical Sciences, Ritsumeikan University, Kusatsu 525-8577, Shiga, Japan.
We have developed transition-metal-free synthetic methodologies for dibenzoxazepinones utilizing salicylamides as starting materials and employing two distinct types of successive hypervalent iodine-mediated arylocyclizations. This synthetic protocol encompasses selective phenol -arylation of salicylamides with diaryliodonium salts, followed by electrophilic aromatic amination utilizing chemically or electronically generated hypervalent iodine reagents in the second stage of the process.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Department of Chemistry and Chemistry Institution for Functional Materials, Pusan National University, Busan 46241, Republic of Korea.
ConspectusControlling selectivity through manipulation of reaction intermediates remains one of the most enduring challenges in organic chemistry, providing novel solutions for selective C-C π-bond functionalization. This approach, guided by activation principles, provides an effective method for selective functional group installation, enabling direct synthesis of organic molecules that are inaccessible through conventional pathways. In particular, the selective functionalization of N-conjugated allenes and alkynes has emerged as a promising research focus, driven by advances in controlling reactive intermediates and activation strategies.
View Article and Find Full Text PDFOrg Lett
January 2025
Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China.
Although methods for synthesizing chiral phosphorus scaffolds are available, the potential of this molecular chirality remains largely unexplored. Herein, we present a remote desymmetrization of prochiral biaryl phosphine oxides through an organocatalytic asymmetric arylation. This metal-free approach enables the efficient synthesis of a wide range of densely functionalized P(V)-stereogenic compounds with good to excellent yields and satisfactory enantioselectivities.
View Article and Find Full Text PDFJ Org Chem
January 2025
School of Pharmacy, Guangdong Pharmaceutical University, Guangzhou 510006, P. R. China.
In this study, a metal-free and efficient method for the synthesis of sulfilimines and -sulfanylanilines in high yields with excellent chemoselectivities from oxonium aryne precursors with sulfenamides has been developed. This method features mild reaction conditions, simple operations, a general substrate scope, and good tolerance of functional groups. In addition, scale-up synthesis, related applications, and preliminary mechanistic explorations were also investigated.
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