Copper Dispersed Covalent Organic Framework for Azide–Alkyne Cycloaddition and Fast Synthesis of Rufinamide in Water

Abstract

A crystalline porous bipyridine‐based Bpy‐COF with a high BET surface area (1864 m2 g−1) and uniform mesopore (4.0 nm) is successfully synthesized from 1,3,5‐tris‐(4’‐formyl‐biphenyl‐4‐yl)triazine and 5,5'‐diamino‐2,2'‐bipyridine via a solvothermal method. After Cu(I)‐loading, the resultant Cu(I)‐Bpy‐COF remained the ordered porous structure with evenly distributed Cu(I) ions at a single‐atom level. Using Cu(I)‐Bpy‐COF as a heterogeneous catalyst, high conversions for cycloaddition reactions are achieved within a short time (40 min) at 25 °C in water medium. Moreover, Cu(I)‐Bpy‐COF proves to be applicable for aromatic and aliphatic azides and alkynes bearing various substituents such as ester, hydroxyl, amido, pyridyl, thienyl, bulky triphenylamine, fluorine, and trifluoromethyl groups. The high conversions remain almost constant after five cycles. Additionally, the antiepileptic drug (rufinamide) is successfully prepared by a simple one‐step reaction using Cu(I)‐Bpy‐COF, proving its practical feasibility for pharmaceutical synthesis.

Precise Modulation of Conjugative Structure and Porosity in Covalent Organic Frameworks for Transition Metal Free Visible-Light Catalysis of Trifluoromethylation

“…Covalent organic frameworks (COFs) are a class of newly emerged porous materials and have exhibited promising applications in chemical syntheses, − photocatalytic water splitting, − hydrogen peroxide synthesis, − CO 2 reduction, − and pollutant degradation. , Conjugated COFs can readily regulate light absorption and electron band by means of the elaborate selection of building units and types of linking bond. Moreover, the π-conjugative and ordered structure with large porosity in COFs facilitates the migration of photogenerated electrons and inhibits electron–hole recombination, whereas the strong covalent bonds impart to COFs good chemical stability for maintaining photocatalytic activity.…”