We report herein a two or three step synthesis of fluorinated π-conjugated oligomers through iterative C-H bond arylations. Palladium-catalyzed desulfitative arylation of heteroarenes allowed in a first step the synthesis of fluoroaryl-heteroarene units in high yields. Then, the next steps involve direct arylation with aryl bromides catalyzed by PdCl(C3H5)(dppb) to afford triad or tetrad heteroaromatic compounds via regioselective activation of C(sp(2))-H bonds.
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http://dx.doi.org/10.3762/bjoc.11.218 | DOI Listing |
Org Biomol Chem
January 2025
School of Chemistry and Chemical Engineering, Guangxi Colleges and Universities Key Laboratory of Applied Chemistry Technology and Resource Development, Guangxi University, Nanning 530004, Guangxi, P. R. China.
We present a mild and efficient method for the arylation of N-H heteroarenes using a low-loading Pd/keYPhos catalyst (0.8 mol%). This approach employs inexpensive and structurally diverse aryl chlorides as electrophiles in reactions with indoles, pyrroles, and carbazole, enabling the construction of a wide range of -arylated products.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
University of Melbourne, School of Chemistry, 30 Flemington Rd., VIC 3095, Parkville, AUSTRALIA.
Palladium(II)-catalyzed C-H functionalization has attracted considerable attention as a pathway to late-stage modification of peptides. Herein, we report the Pd-catalyzed C(sp3)-H arylation of peptides directed by an amidoxime ether, which can be easily incorporated into peptides at any amide bond. Site- and stereoselective arylation of peptides has been achieved, including an unprecedented example of C-H arylation of an internal residue.
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 Biomol Chem
January 2025
School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China.
A variety of α-arylated sulfoxonium ylides could be facilely synthesized in modest to high yields through α-arylation of sulfoxonium ylides with aryl fluorosulfates C-O bond functionalization under palladium catalysis. Reactions using readily available and bench-stable aryl fluorosulfates as effective and appealing arylating agents showed both good substrate scope and broad functionality tolerance. Important functional groups such as nitro, cyano, formyl, acetyl, methoxycarbonyl, trifluoromethoxy, fluoro, and chloro embedded in substrates remained intact during the course of the reaction, and could be subjected to downstream modification.
View Article and Find Full Text PDFOrg Lett
December 2024
Biomimetic Catalysis, Catalysis Research Center, TUM School of Natural Sciences, Technical University of Munich, Lichtenbergstrasse 4, 85748 Garching, Germany.
Inspired by natural cryptic halogenation in -bond formation, this study developed a synthetic approach combining biocatalytic bromination with transition-metal-catalyzed cross-coupling. Using the cyanobacterial VHPO, a robust and sustainable bromination-arylation cascade was created. Genetic modifications allowed enzyme immobilization, enhancing the compatibility between biocatalysis and chemocatalysis.
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