An organoelectrophotocatalytic approach for the C-H silylation of heteroarenes through dehydrogenation cross-coupling with H evolution has been developed. The organoelectrophotocatalytic strategy is carried out under a simple and efficient monocatalytic system by employing 9,10-phenanthrenequinone both as an organocatalyst and as a hydrogen atom transfer (HAT) reagent, which avoids the need for an external HAT reagent, an oxidant, or a metal reagent. A variety of heteroarenes can be compatible in satisfactory yields with excellent regioselectivity.
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http://dx.doi.org/10.1021/acs.orglett.3c00144 | DOI Listing |
Org Lett
January 2025
Department of Biophysical Chemistry, Graduate School of Pharmaceutical Science, Tohoku University, AobaSendai 980-8578, Japan.
In this paper, we report that the use of an alkyl silyl carbonate reagent combined with CsF and 18-crown-6 facilitates efficient direct carboxylations of (hetero)aromatic C-H bonds. This system also enables benzylic carboxylation of a toluene derivative and double carboxylation of methyl heteroarene. The carbonate reagent is characterized by its ease of handling and storage.
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January 2025
Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Key Laboratory of Research and Development for Natural Products, School of Pharmacy, Yunnan University Kunming 650500 P. R. China
Hydrogen atom transfer (HAT) processes provide an important strategy for selective C-H functionalization. Compared with the popularity of 1,5-HAT processes, however, net-1,2-HAT reactions have been reported less frequently. Herein, we report a unique visible-light-mediated net-1,2-HAT of amidyl radicals for the synthesis of β-amido ketone derivatives.
View Article and Find Full Text PDFACS Cent Sci
November 2024
Department of Chemistry, University of California, Berkeley, California 94720, United States.
Angew Chem Int Ed Engl
November 2024
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing, 401331, P. R. China.
A facile photochemical, one-pot synthesis of highly functionalized 1-aminotetralins derivatives (>70 examples) from readily accessible o-alkyl and o-formyl aryl silylimines with olefins is described. A diradical-mediated hydrogen atom transfer (DHAT) of primary, secondary, and tertiary C(sp)-H bonds of o-alkyl arylsilylimines and C(sp)-H bonds of o-formyl arylsilylimines enabled a [4+2] annulation with olefins in excellent diastereoselectivity. This was accomplished upon irradiation at λ = 420 nm in the presence of thioxanthen-9-one (10 mol %) as the sensitizer via energy transfer.
View Article and Find Full Text PDFNat Commun
August 2024
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, P. R. China.
Nickel-catalyzed C-H bond functionalization reactions provide an impressive alternative to those with noble metal catalysts due to their unique reactivity and low cost. However, the regioselective C(sp)-H borylation reaction of arenes accomplished by nickel catalyst remains limited. We herein disclose a silyl-directed ortho C(sp)-H borylation of substituted arenes with a Ni(cod)/PMe/KHMDS catalyst system.
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