5-Hydroxymethylfurfural-Derived Boron-Dipyrromethene Immobilized on Resin Support as a Sustainable Catalyst for C–H Arylation of Heterocycles

Abstract

5-Hydroxymethylfurfural (HMF) was used as a sustainable raw material in the development of a resin-supported boron-dipyrromethene (BODIPY)-based photocatalyst. In the development of the catalyst, the brominated product (HMF-BODIPY-Br) and photocatalyst (HMF-BODIPY-Br-Suc) were isolated under a chromatography-free condition. The photocatalyst was loaded on polymeric resin by bridging alcohol functionality in HMF and amine functionality in polymeric resin using succinic anhydride. The resin-supported photocatalyst was used in light-mediated C–H arylation of various heterocycles using aryldiazonium salt. For representative examples, diazotization and photoarylation were carried out in one pot, and arylated furans were obtained in very good yields. C–H arylation was found to proceed via a photogenerated radical intermediate, and the radical intermediate was trapped by forming an adduct with TEMPO.

State of the Art of Bodipy‐Based Photocatalysts in Organic Synthesis

“…More recently, Vairaprakash developed a 5‐hydroxymethylfurfural‐derived Bodipy immobilized on resin support as a catalyst for the arylation of (hetero)arenes with aryl diazonium salts (Figure 3). [37] …”

“…More recently, Vairaprakash developed a 5-hydroxymethylfurfural-derived Bodipy immobilized on resin support as a catalyst for the arylation of (hetero) arenes with aryl diazonium salts (Figure 3). [37] The dibromo-Bodipy framework was prepared from the raw material 5-hydroxymethylfurfural (HMF) derived from fructose and the dye was immobilized on a polymeric resin. In this report, the catalyst B10 enabled the arylation of furan, thiophene, and benzene with diversely substituted aryl diazonium salts under green light irradiation.…”

A sustainable pseudo-homogeneous catalyst from renewable biomass: design, development and catalytic applications

“…We have previously studied the application of 1,3,7,9-tetramethyl-5-aryldipyrromethanes as chemosensors 41,42 and also utilized 1,3,7,9-tetramethyl-5-furanyldipyrromethane in the preparation of BODIPY based photocatalysts. 43 Unsubstituted DPMs were utilized in the development of bis(dipyrrinato)zinc complexes and various tetrapyrrolic macrocycles, including porphyrins, chlorins, etc. [44][45][46] In the synthesis of tetra-substituted DPMs using res-HMF-Cu as a catalyst, the reactions were very clean and the expected product tetramethyl-substituted DPM alone formed.…”