72709-31-0Relevant articles and documents
Triarylamine-based porous coordination polymers performing both hydrogen atom transfer and photoredox catalysis for regioselective α-amino C(sp3)-H arylation
Li, Hanning,Yang, Yang,Jing, Xu,He, Cheng,Duan, Chunying
, p. 8512 - 8520 (2021)
Direct functionalization of C(sp3)-H bonds in a predictable, selective and recyclable manner has become a central challenge in modern organic chemistry. Through incorporating different triarylamine-containing ligands into one coordination polymer, we present herein a heterogeneous approach to the combination of hydrogen atom transfer (HAT) and photoredox catalysis for regioselective C-H arylation of benzylamines. The different molecular sizes and coordination modes of the ligands, tricarboxytriphenylamine (H3TCA) and tris(4-(pyridinyl)phenyl)amine (NPy3), in one coordination polymer consolidate the triarylamine (Ar3N) moiety into a special structural intermediate, which enhances the chemical and thermal stability of the polymers and diminishes structural relaxation during the catalytic process. The inherent redox potentials of Ar3N moieties prohibit thein situformed Ar3N˙+to earn an electron from C(sp3)-H nucleophiles, but allow the abstraction of a hydrogen atom from C(sp3)-H nucleophiles, enabling the formation of the C(sp3)˙ radical and the cross-coupling reaction to proceed at the most electron-rich sites with excellent regioselectivity. The new heterogeneous photoredox HAT approach skips several interactions between transient species during the typical synergistic SET/HAT cycles, demonstrating a promising redox-economical and reagent-economical heterogeneous platform that has not been reported for α-amino C-H arylation to form benzylamine derivatives. Control experiments based on monoligand coordination polymers suggested that the mixed-ligand approach improved the photochemical and photophysical properties, providing important insight into rational design and optimization of recyclable photocatalysts for rapid access to complex bioactive molecules and late-stage functionalized pharmaceuticals.
One-step Synthesis of Cyclic Compounds by Electrochemical Reduction of Unsaturated Compounds in the Presence of Dielectrophiles
Degrand, Chantal,Compagnon, Paul-Louis,Belot, Gerard,Jacquin, Dominique
, p. 1189 - 1196 (2007/10/02)
The one-step synthesis of cyclic compounds is achieved in a few cases by electroreduction of unsaturated compounds in DMF, at a mercury pool cathode, in the presence of a more difficulty reducible dielectrophile.Unsaturated compounds include activated olefins, aromatic Schiff bases, ketones, and azo, nitroso, and nitro compounds.Four dielectrophiles are used; they are tri- or tetramethylene bromide, succinyl chloride, and 4-bromobutyryl chloride.The electrochemical synthesis of derivatives of cyclohexane, piperidine, pyrrolidine, hexahydropyridazine, tetrahydropyridazinone, tetrahydropyridazinedione, tetrahydrooxazine, isoxazolidine, and spirolactone can be succesfully performed.Their yields range from 8 to 78percent depending on competitive reactions.Results of chemical reduction by alkali metals and electrochemical reduction are compared.
