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Nickel catalysts of chiral pyrox ligands promoted enantioselective reductive arylation and heteroarylation of aldimines, using directly (hetero)aryl halides and sulfonates. The catalytic arylation can also be conducted with crude aldimines generated from condensation of aldehydes and azaaryl amines. Mechanistically, density functional theory (DFT) calculations and experiments pointed to an elementary step of 1,4-addition of aryl nickel(I) complexes to -azaaryl aldimines.
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http://dx.doi.org/10.1021/jacs.3c00548 | DOI Listing |
Angew Chem Int Ed Engl
September 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
The enantioselective construction of quaternary carbon stereocenters bearing amine functionalities represents a significant challenge in organic synthesis despite their prevalence in pharmaceutically active compounds. Herein, we report a versatile metallaphotoredox platform for the asymmetric incorporation of amine fragments onto quaternary carbons via coupling of alkene-tethered aryl bromides with readily available α-silylamines. This transformation proceeds under mild conditions without requiring organometallic reagents or stoichiometric reductants.
View Article and Find Full Text PDFOrg Lett
September 2025
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P. R. China.
Using the chiral -manganese complex as catalyst, asymmetric hydrogenation of multi-nitrogen aromatic heterocycles including 5- or 7-substituted pyrazolo[1,5-]pyrimidines, pyrrolo[1,2-]pyrazines, and imidazo[1,2-]pyrazines has been successfully developed, providing the corresponding reductive products with high enantioselectivity, reactivity, and wide substrate scope.
View Article and Find Full Text PDFNat Catal
July 2025
Department of Chemistry, The Scripps Research Institute; 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.
Despite increasing demand for chiral fluorinated organic molecules, enantioselective C-H fluorination remains among the most challenging and sought-after transformations in organic synthesis. Furthermore, utilizing nucleophilic sources of fluorine is especially desirable for F-radiolabelling. To date, methods for enantioselective nucleophilic fluorination of inert C(sp)-H bonds remain unknown.
View Article and Find Full Text PDFJACS Au
August 2025
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
An efficient kinetic resolution of ferroceno-[]-isoquinolines was realized through chiral phosphoric acid-catalyzed asymmetric transfer hydrogenation, affording the planar-chiral ferroceno-[]-isoquinolines and planar-chiral -butyl ferroceno-[]-isoquinoline-4-(5)-carboxylates with a selectivity factor of up to 58. The -Boc group could be easily removed from the reductive product. Moreover, the recovered materials could be transformed into various planar-chiral ferrocene-based bidentate ligands, which were successfully applied in several asymmetric catalytic reactions with excellent yields and enantioselectivities.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
We report herein an enantioselective total synthesis of (-)-psathyrin A, an antibacterial diterpene natural product possessing a unique 6/4/5/5 tetracyclic carbon skeleton and seven contiguous stereocenters, including three adjacent all-carbon quaternary centers. Our synthesis begins with commercially available 2-methyl-2-cyclopenten-1-one, which was subjected to an enantioselective copper/NHC-catalyzed conjugate addition, followed by trapping the resulting enolate with 1-bromo-2-butyne to set up the first two stereocenters, including one all-carbon quaternary center. A Suzuki-Miyaura cross coupling introduces an aromatic ring as the six-membered ring precursor, and a gold(I)-catalyzed Conia-ene reaction constructs the 5/5-fused bicyclic ring system and the second all-carbon quaternary center.
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