Nano CoCuFe₂O₄‐catalyzed coupling reaction of arylboronic acid with amines and thiols: An atom‐economic and ligand‐free route to access unsymmetrical amines and sulfides

Abstract

An efficient protocol was developed for the nano CoCuFe 2 O 4 -catalyzed C-N and C-S bond formation. By this catalytic system, both amine and sulfide-based structural motifs were formed efficiently in aryl halide-free route. The amination reaction of phenyl boronic acid with various types of amines was conducted under ligand-free conditions, in ethanol as a green solvent at 60°C. Unsymmetrical diaryl/aryl alkyl sulfide synthesis via the coupling reaction of arylboronic acids with thiols was also conducted. The nano cobalt-copper ferrite was used as a heterogenous efficient, inexpensive, magnetically separable and recyclable catalyst that can be used for several cycles.

Recent Advances in the Synthesis of Sulfides, Sulfoxides and Sulfones via C-S Bond Construction from Non-Halide Substrates

“…The final C-S coupling reaction of phenyl radical and disulfide afforded the products. In 2019, the Moghaddam group developed a coupling reaction of arylboronic acid with aryl or alkyl thiols to prepare unsymmetrical sulfides using CoCuFe 2 O 4 nanoparticles as catalyst (Scheme 26) [46]. The reaction proceeded in the presence of n-Bu 4 NOH in DMF at 100 • C. This protocol was also applied in the C-N coupling reaction of arylboronic acid and anilines.…”

Symmetrical Tertiary Amines: Applications and Synthetic Approaches

“…In 2018 Moghaddam and co‐authors developed CoCuFe 2 O 4 nanoparticles and applied them as a catalyst for the Ullmann‐type reaction. [ 342 ] 5 mol‐% of this catalyst in combination with KOH at 60 °C allows to prepare Ph 3 N from Ph 2 NH and phenylboronic acid in 85 % yield.…”

Green synthesis of shape-tunable CuFe2O4NPs: a magnetically retrievable and efficient catalyst for Chan–Lam type C–N coupling reactions under base-free conditions

“…16 To combat the recovery, and hence the reusability issues, heterogeneous catalysts are extensively used under various reaction conditions for C-N coupling reactions. [17][18][19][20][21][22][23][24] However, prolonged reaction time, high temperature, use of ligands and base, the necessity of a support for the active catalyst for better performance and the tedious synthesis procedure for the catalyst are again the most common drawbacks. These inconveniences invite researchers to develop an easy but effective protocol for the C-N coupling reactions.…”

“…Among different heterogeneous catalysts, magnetic nanocatalysts have emerged as effective catalysts because of their unique magnetic properties, lower operational costs, easy accessibility and recovery from the reaction mixture, easy recyclability and chemical stability. [18][19][20][21][24][25][26][27] In recent years, ferrite-based magnetic NPs have gained considerable attention from researchers in the field of heterogeneous catalysis over other magnetic NPs due to their low cost, low toxicity, excellent reaction output, ease of recovery for reuse without significant loss of activity, and compatibility with green chemistry aspects. 25,[28][29][30][31] Among different magnetic ferrite NPs, CuFe 2 O 4 NPs have many technological advantages due to their phase transition, high air-stability, changing semiconducting properties, tetragonality, and electrical switching variation when treated under various conditions, as well as interesting electrical and magnetic properties with thermal and chemical stabilities.…”

“…35,36 Accordingly, several research groups have used CuFe 2 O 4 NPs extensively as catalysts in organic synthesis. 21,32,33,[37][38][39][40] These reports motivated us to use CuFe 2 O 4 NPs as reusable and effective catalysts for a Chan-Lam type C-N coupling reaction under mild conditions. To the best of our knowledge, no effort has been made so far toward the Chan-Lam type C-N bond-forming reactions using CuFe 2 O 4 NPs as catalysts.…”