Magnetically recoverable catalysts for efficient multicomponent synthesis of organosulfur compounds

Abstract

This manuscript introduces a groundbreaking study on the development and application of magnetically recoverable catalysts for the efficient multicomponent synthesis of organosulfur compounds. Capitalizing on the unique advantages of magnetic recovery, these catalysts streamline the synthesis process, offering an innovative solution that marries efficiency with environmental sustainability. By facilitating the multicomponent reaction of key precursors in the presence of sulfur sources, the catalysts enable the straightforward synthesis of various valuable organosulfur compounds, crucial in numerous pharmaceutical, agricultural, and material science applications. Key findings demonstrate a significant enhancement in reaction yields and selectivity and the remarkable ease with which the catalysts can be recovered and reused, thereby reducing both waste and operational costs. Magnetic catalysts, often based on magnetic iron nanoparticles, facilitate rapid and efficient reactions under mild conditions, offering superior atom economy, reduced solvent use, and the potential for scalable processes. Additionally, magnetically separating the catalysts from the reaction mixture enables multiple recycling cycles, reducing waste and operational costs. The review also discusses the mechanistic insights, challenges, and recent advancements in this field alongside future directions for developing more robust and versatile magnetic catalytic systems. This research embodies a significant step forward in the field of catalysis, highlighting the potential of magnetically recoverable catalysts to revolutionize the synthesis of complex molecules. Future perspectives discussed in the manuscript focus on expanding the scope of these catalysts to broader applications, optimizing catalyst design for enhanced performance, and further aligning chemical synthesis processes with the principles of green chemistry. This review covers the literature from 2010 to the end of 2024, and it encompasses the different one-pot protocols for synthesizing various heterocyclic organosulfur compounds based on magnetically recoverable catalysts.

Fig. 1. Highlights of magnetic catalysts.

Fig. 2. Some important molecules containing sulfide scaffold.

Fig. 3. Magnetic catalysts in multicomponent preparation of organosulfur compounds.

Fig. 4. The advantages and disadvantages of magnetically recoverable catalysts.

Fig. 5. Structure of several magnetic catalysts in preparation of sulfides.

Scheme 1. Fe₃O₄@AMBA-CuI (MRC-1) catalyzed synthesis of heteroaryl-aryl and di-heteroaryl sulfides from S₈.

Scheme 2. CuFe₂O₄ NPs (MRC-2) catalyzed synthesis of benzothiazole or benzoxazole-sulfide aryls from S₈.

Scheme 3. Fe₃O₄@ABA-aniline-CuI nanomaterial (MRC-3) catalyzed preparation of benzothiazole sulfides from CS₂.

Scheme 4. Fe₃O₄@SiO₂-ABHA-CuCl nanomaterial (MRC-4) catalyzed synthesis of diaryl sulfides infused with intricate imidazo[1,2-a]pyridine scaffolds from S₈.

Scheme 5. Fe₃O₄@BTH-Pyr-CuCl nanomaterial (MRC-5) catalyzed synthesis of heteroaryl-aryl sulfides from sulfur.

Fig. 6. Several bioactive examples of thioester molecules.

Fig. 7. Structure of magnetic catalysts in MRCs synthesis of thioesters.

Scheme 6. Fe₃O₄@BA/Pyrim-carboxamide-NiCl₂ (MRC-6) catalyzed preparation of thioesters from thiols.

Scheme 7. rGO/Fe₃O₄–CuO (MRC-7) catalyzed preparation of thioesters from thiols.

Fig. 8. Several examples of bioactive compounds based on the thiazole structure.

Scheme 8. Fe₂O₃ nanoparticles (MRC-8) catalyzed preparation of isatin-thiazole derivatives from thiosemicarbazide.

Scheme 9. Fe₂O₃ nanoparticles (MRC-9) catalyzed preparation of hydrazinyl thiazole derivatives from thiosemicarbazide.

Fig. 9. Structure of magnetic catalysts in MCRs synthesis of thiazoles and benzothiazoles.

Scheme 10. Fe₃O₄@vitamin B1 nanomaterial (MRC-10) catalyzed preparation of trisubstituted 1,3-thiazole derivatives from thioamides.

Scheme 11. Fe₃O₄@CeO₂ nanomaterial (MRC-11) catalyzed preparation of thiazole derivatives from thiosemicarbazide.

Scheme 12. ZnS–ZnFe₂O₄ nanomaterial (MRC-12) catalyzed preparation of pyridazinone-thiazole derivatives from thiosemicarbazide.

Fig. 10. Several bioactive examples of benzothiazole molecules.

Scheme 13. Fe₃O₄@SiO₂-(imine-thiazole)-Cu(OAc)₂ nanomaterial (MRC-13) catalyzed preparation of 2-substituted benzothiazole derivatives from S₈.

Scheme 14. Cu(0)-Fe₃O₄@SiO₂/NH₂cel nanomaterial (MRC-14) catalyzed preparation of 2-aryl benzothiazole derivatives from thiourea.

Scheme 15. Fe₃O₄@DOP-amide/Imid-CuCl₂ nanomaterial (MRC-15) catalyzed preparation of 2-aryl benzothiazole derivatives from thiourea.

Fig. 11. Several bioactive examples of sulfonamide molecules.

Fig. 12. Structure of magnetic catalysts in MCRs synthesis of sulfonamides.

Scheme 16. Fe₃O₄@dopamine-PO-CuBr₂ (MRC-16) catalyzed preparation of N-aryl sulfonamides from DABSO.

Scheme 17. MNPs-benzo[d]imidazole-Cu (MRC-17) catalyzed preparation of sulfonamides from DABSO.

Scheme 18. Fe₃O₄@arginine-Pd(0) (MRC-18) catalyzed preparation of N-aryl sulfonamides from K₂S₂O₅.

Scheme 19. Fe₃O₄@DAPA-Pd(0) (MRC-19) catalyzed preparation of sulfonamides from SO₂.

Scheme 20. Fe₃O₄@SiO₂-picolylamine-Pd (MRC-20) catalyzed preparation of sulfonamides from DABSO.

Fig. 13. Several bioactive examples of sulfone molecules.

Fig. 14. Structure of magnetic catalysts in MCRs synthesis of diaryl sulfones.

Scheme 21. Fe₃O₄@DABA-PA-CuBr₂ nanomaterial (MRC-21) catalyzed preparation of diaryl sulfone derivatives from DABSO.

Scheme 22. Fe₃O₄@SiO₂-imine/Thio-Cu(ii) nanomaterial (MRC-22) catalyzed preparation of diaryl sulfone derivatives from DABSO.

Scheme 23. Fe₃O₄@BBI-CuBr nanomaterial (MRC-23) catalyzed preparation of diaryl sulfone derivatives from DABSO.

Mosstafa Kazemi

Ramin Javahershenas