Herein, an efficient visible-light-mediated N-H heteroarylation via remote heteroaryl ipso-migration has been accomplished. Moderate to good yields were obtained with good functional group tolerance. Moreover, a simple and readily available organic photoredox catalyst was employed, avoiding the use of complex and costly noble metal compounds.
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http://dx.doi.org/10.1039/d0ob01594f | DOI Listing |
Chem Commun (Camb)
November 2024
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
The direct functionalization of remote C(sp)-H is valuable but challenging, and is even more difficult to achieve than the γ-C(sp)-H functionalization of alcohols. Among the strategies, hydrogen atom transfer (HAT) is one of the solutions for such transformations. Herein, we designed a migration reaction involving carbon monoxide, forming an alkoxy radical by photocatalysis, and used carbon monoxide to extend the carbon chain to provide a site for the migration of heteroaryl groups, which makes 1,4-HAT more advantageous, and we relied on this strategy to successfully achieve the synthesis of 1,4-dicarbonyl compounds by γ-C(sp) functionalization of alcohols.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
State Key Laboratory for Quality Ensurance and Sustainable Use of Dao-di Herbs, Institute of Medicinal Plant Development, Chinese Academy of Medical Science & Peking Union Medical College, Beijing, 100193, China.
The molecular engineering of boron dipyrromethenes (BODIPYs) has garnered widespread attention due to their structural diversity enabling tailored physicochemical properties for optimal applications. However, catalytic enantioselective synthesis of structurally diverse boron-stereogenic BODIPYs through intermolecular desymmetrization and BODIPYs with atroposelectivity remains elusive. Here, we showcase rhodium(II)-catalyzed site-specific C-H (hetero)arylations of prochiral BODIPYs and polysubstituted BODIPYs with diazonaphthoquinonesand diazoindenines, providing efficient pathways for the rapid assembly of versatile (hetero)arylated boron-stereogenic and axially chiral BODIPYs through long-range desymmetrization and axial rotational restriction modes.
View Article and Find Full Text PDFChem Asian J
December 2024
Hebei Normal University for Nationalities, Chengde, Hebei Province, China.
A copper-catalyzed trifunctionalization (trifluoromethylation, heteroarylation, and cyanation) of heteroaryl-substituted 1-hexenes via remote heteroaryl migration is reported. A variety of CF and heteroaryl-containing nitriles were readily constructed under mild conditions. The reaction features high chemo- and regioselectivities and represents a convenient method for the synthesis of multifunctionalized molecules in organic synthesis.
View Article and Find Full Text PDFNat Chem
October 2024
Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China.
Chem Sci
August 2024
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences 116023 Dalian Liaoning China
Carbonylative transformation represents one of the most straightforward procedures for the synthesis of carbonyl-containing compounds. However, the carbonylative procedure toward 1,4-diketones is still limited which are key moieties with potent applications in various areas. Herein, we report a new strategy for the synthesis of multi-carbonyl compounds containing a 1,4-diketone skeleton through remote heteroaryl migration of traditionally restricted 1,3-migratory substrates utilizing carbon monoxide (CO) as the C1 synthon and diazonium compounds as the starting material.
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