C-H functionalization of aliphatic carboxylic acids without attaching exogenous auxiliary has been so far limited at the proximal β-position. In this work, we demonstrate a ligand enabled palladium catalyzed first regioselective distal γ-C(sp3)-H functionalization of aliphatic carboxylic acids without incorporating an exogenous directing group. Aryl iodides containing versatile functional groups including complex organic molecules are well tolerated with good to excellent yields during the γ-C(sp3)-H arylation reaction. Interestingly, weak coordination of carboxylate group can be further extended for sequential hetero di-arylation. Application of the protocol has been showcased by synthesizing substituted α-tetralone. Mechanistic investigations have been carried out to shed light on the reaction pathway.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1002/anie.201907262 | DOI Listing |
Molecules
January 2025
Sustainable Chemistry for Metals and Molecules, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium.
A pyridine-fused triazapentalene shows weak fluorescence in solution and is readily accessible via nitrene-mediated cyclization. In this study, a modified Cadogan reaction was used to synthesize . Palladium-catalyzed reactions have been used as post-functionalization methods.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, University of Houston, Houston, Texas 77204-5003, United States.
Monoanionic, bidentate-auxiliary-directed, cobalt-catalyzed C-H bond functionalization has become a very useful tool in organic synthesis. A comprehensive investigation into isolated organometallic intermediates and their reactivity within the catalytic cycle is lacking. We report here mechanistic studies of cobalt-catalyzed, aminoquinoline-directed C(sp)-H bond functionalization.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, School of Science, China Pharmaceutical University, Nanjing 211198, People's Republic of China.
The development and enantioselective synthesis of two types of -symmetric spirobi[dihydrophenalene] structures is reported. The reaction proceeds via rhodium-catalyzed 2-fold asymmetric conjugate arylation of dienones followed by BF·OEt-promoted spirocyclization to give the enantiopure spiro products. Additive-dependent chemodivergent synthesis of 3,3'-diarylated 2,2',3,3'-tetrahydro-1,1'-spirobi[phenalene]-9,9'-diols (3,3'-Ar-SPHENOLs) and the corresponding spiro diary ethers from the same intermediate is achieved.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Shanghai Inst Org Chem, State Key Lab Organometallic Chem, 345 Lingling Lu, 200032, Shanghai, CHINA.
Rhodium-catalyzed regio- and enantioselective allylic arylation of racemic alkyl- and aryl- substituted allylic carbonates with arylboronic acids using commercially available BIBOP ligand is reported. This reaction proceeds at room temperature without base or other additive to deliver allylic arylation products in excellent yields, regio- and enantioselectivity (up to 95% yield, >20:1 b/l, >99% ee). Rh/BIBOP is disclosed as an efficient catalytic system for allylic substitution reaction.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China.
A visible-light-promoted azidation/arylation of unactivated alkenes with Togni-N has been achieved, leading to a series of azidated pyrrolo[1,2-]indoles under photocatalyst-free conditions. Notably, an EDA complex derived from the electron-rich indole derivatives and Togni-N served as the key intermediate in this reaction.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!