A nickel complex of chiral bisoxazolines catalyzed the stereoselective reductive arylation of ketones in high enantioselectivity. A range of common acyclic and cyclic ketones reacted without the aid of directing groups. Mechanistic studies using isolated complex of a chiral bis(oxazoline) (L)Ni(Ar)Br revealed that Mn reduction was not needed, while Lewis acidic titanium alkoxides were critical to ketone insertion.
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http://dx.doi.org/10.1021/jacs.4c02818 | DOI Listing |
Chemistry
January 2025
The University of Electro-Communications: Denki Tsushin Daigaku, Department of Engineering Science, JAPAN.
(6,5)-enriched single-walled carbon nanotubes (SWCNTs) were reductively arylated using sodium naphthalenide and monosubstituted and disubstituted iodobenzene derivatives to control their photoluminescence (PL) properties. In the reactions with substituted iodobenzenes, the degree of functionalization was influenced by the substituents on the aryl groups depending on their position, which allowed us to realize control of the PL intensity. The substituents at the 2-position and methyl groups at the 3,5-positions of the phenyl group respectively increased the E11** PL and E11* PL selectivity at ~1230 and ~1100 nm.
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 Biomol Chem
January 2025
Center for Supramolecular Chemistry and Catalysis and Department of Chemistry, Shanghai University, 99 Shang-Da Road, Shanghai 200444, China.
Herein, we report a Ni-catalyzed cross-electrophile coupling of aryl/vinyl halides with benzothiazolium salts derived from alcohols. Our findings demonstrate that primary alkyl benzothiazolium salts serve as effective C(sp)-O substrates, facilitating coupling with aryl and vinyl halides. This method not only enables the formal functionalization of primary alcohols but also provides experimental support for previously established sequential alcohol halogenation and Ni-catalyzed reductive coupling platforms.
View Article and Find Full Text PDFOrg Lett
December 2024
School of Chemical Engineering and Technology, Guangdong Engineering Technology Research Center for Platform Chemicals from Marine Biomass and Their Functionalization, Sun Yat-sen University, Zhuhai 519082, P. R. China.
A novel protocol for the Cu-catalyzed reductive -arylation of nitroarenes with (hetero)aryl chlorides in water has been realized. Combining -(9-carbazol-9-yl)-6-hydroxypicolinamide () with oxalohydrazide is vital to realize the method at 90 °C with a loading of 5 mol % of CuO/. Various nitroarenes and aryl chlorides have been successfully coupled in good to excellent isolated yields.
View Article and Find Full Text PDFOrg Lett
December 2024
Department of Chemistry and Biochemistry and California NanoSystems Institute, University of California, Los Angeles, California 90095-1569, United States.
Oxidant-free Au(I)/Au(III)-catalyzed cross-coupling has been recently enabled by the use of bidentate ,-ligands. To further develop these ,-ligands, computational studies were performed to understand their effects on the oxidative addition of aryl iodide electrophiles with Au(I). Using this mechanistic understanding, six new electron-rich ,-ligands were synthesized.
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