Site-Specific C(sp3 )-H Aminations of Imidates and Amidines Enabled by Covalently Tethered Distonic Radical Anions.

The utilization of N-centered radicals to synthesize nitrogen-containing compounds has attracted considerable attention recently, due to their powerful reactivities and the concomitant construction of C-N bonds. However, the generation and control of N-centered radicals remain particularly challenging. We report a tethering strategy using SOMO-HOMO-converted distonic radical anions for the site-specific aminations of imidates and amidines with aid of the non-covalent interaction. This reaction features a remarkably broad substrate scope and also enables the late-stage functionalization of bioactive molecules. Furthermore, the reaction mechanism is thoroughly investigated through kinetic studies, Raman spectroscopy, electron paramagnetic resonance spectroscopy, and density functional theory calculations, revealing that the aminations likely involve direct homolytic cleavage of N-H bonds and subsequently controllable 1,5 or 1,6 hydrogen atom transfer.

Trichloroacetonitrile as an efficient activating agent for the ipso-hydroxylation of arylboronic acids to phenolic compounds.

A metal-free and base-free Cl3CCN mediated method was developed for the ipso-hydroxylation of aryl boronic acids to their corresponding phenols, which was promoted by a key unstable Lewis adduct intermediate. This transformation has broad functional group tolerance, and late-stage functionalization was successful as well. After simple investigation, two pathways (radical/ionic mechanism) were suggested, and the beneficial action of blue light needs to be further studied.

Design and synthesis of broadband absorption covalent organic framework for efficient artificial photocatalytic amine coupling.

Developing highly active materials that efficiently utilize solar spectra is crucial for photocatalysis, but still remains a challenge. Here, we report a new donor-acceptor (D-A) covalent organic framework (COF) with a wide absorption range from 200 nm to 900 nm (ultraviolet-visible-near infrared light). We find that the thiophene functional group is accurately introduced into the electron acceptor units of TpDPP-Py (TpDPP: 5,5'-(2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo [3,4-c]pyrrole-1,4-diyl)bis(thiophene-2-carbaldehyde), Py: 1,3,6,8-tetrakis(4-aminophenyl)pyrene) COFs not only significantly extends its spectral absorption capacity but also endows them with two-photon and three-photon absorption effects, greatly enhancing the utilization rate of sunlight. The selective coupling of benzylamine as the target reactant is used to assess the photocatalytic activity of TpDPP-Py COFs, showing high photocatalytic conversion of 99% and selectivity of 98% in 20 min. Additionally, the TpDPP-Py COFs also exhibit the universality of photocatalytic selective coupling of other imine derivatives with ~100% conversion efficiency. Overall, this work brings a significant strategy for developing COFs with a wide absorption range to enhance photocatalytic activity.

Tandem Radical Cyclization for the Construction of Difluoro-Containing Oxindoles and Quinoline-2,4-diones.

Cu-catalyzed direct difluoromethylation of activated alkenes through a difluoromethyl radical addition/cyclization to afford difluorinated oxindoles and quinoline-2,4-diones has been developed. This method provides convenient access to a variety of oxindoles and quinoline-2,4-diones under mild conditions via a proposed tandem radical cyclization process, while tolerating various functional groups well. Moreover, a facile method to construct diverse difluorinated quinoline-2,4-diones by visible-light photoredox catalysis under mild conditions was presented.