A regioselective radical C-H trifluoromethylation of aromatic compounds was developed using cyclodextrins (CDs) as additives. The C-H trifluoromethylation proceeded with high regioselectivity to afford the product in good yield, even on the gram scale. In the presence of CDs, some substrates underwent a single trifluoromethylation selectively, whereas mixtures of single- and double-trifluoromethylated products were formed in the absence of the CD. H NMR experiments indicated that the regioselectivity was controlled by the inclusion of a substrate inside the CD cavity.
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http://dx.doi.org/10.1021/acs.orglett.1c01259 | DOI Listing |
Org Lett
December 2024
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, Jiangxi 330031, People's Republic of China.
A photocatalysis-involved α-amino radical provides an appealing approach for rapid construction of complex amine architectures. Reported herein is an organophotoredox catalytic approach to α-C-H alkylation and heteroarylation of benzyl anilines, which enables the introduction of valuable trifluoromethyl alcohol, chromanone, or pyridine motifs at the α position of amines. This protocol highlights metal-free, step and atom economies and broad substrate scopes (>80 examples).
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December 2024
School of Pharmacy, Xi'an Jiaotong University, Xi'an, Shaanxi 710061, China.
J Am Chem Soc
December 2024
Departamento de Química and Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible, Universidad de Huelva, Huelva 21007, Spain.
In this mixed computational and experimental study, we report a catalytic system for alkane C-C functionalization in which the responsible step for C-H bond activation shows no barrier in the potential energy path. DFT modeling of three silver-based catalysts and four diazo compounds led to the conclusion that the TpAg═C(H)CF (Tp = fluorinated trispyrazolylborate ligand) carbene intermediates interact with methane without a barrier in the potential energy surface, a prediction validated by experimentation using N═C(H)CF as the carbene source. The array of alkanes from propane to -hexane led to the preferential functionalization of the primary sites with unprecedented values of selectivity for an acceptor diazo compound.
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December 2024
State Key Laboratory of Antiviral Drugs, Pingyuan Laboratory, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, China.
Org Lett
November 2024
Department of Natural Products, National Institute of Pharmaceutical Education and Research - Ahmedabad, Gandhinagar, Gujarat 382355, India.
Menadione and its structural analogues are important motifs present in various bioactive natural products and drugs with a wide range of biological activities. In addition, β-trifluoromethyl enone has been employed as an efficient fluorinated building block for the synthesis of CF-containing organic scaffolds. Herein, we report both C-H alkenylation and C-H alkylation reactions using β-CF enones as coupling partners with amino-substituted menadiones under Rh(III) catalysis.
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