A comprehensive review on carbonylation reactions: catalysis by magnetic nanoparticle-supported transition metals

Abstract

Magnetic catalysts have become a crucial innovation in carbonylation reactions, providing a sustainable and highly efficient means of synthesizing compounds that contain carbonyl groups. This review article explores the diverse and significant role of magnetic catalysts in various carbonylation processes, emphasizing their essential contributions to improving reaction rates, selectivity, and recyclability of catalysts. The distinctive magnetic properties of these catalysts enable straightforward separation and recovery, a feature that significantly mitigates waste and reduces environmental impact. As a result, magnetic catalysts' environmental and economic advantages position them as key players in contemporary synthetic chemistry, driving the evolution of green chemistry practices. Particularly noteworthy is the combination of magnetic nanoparticles with transition metals, resulting in the development of robust catalytic systems that exploit the complementary effects of magnetism and catalysis. Recent advances have showcased the adaptability of magnetic nanoparticles supported by transition metal catalysts in various carbonylation reactions, including carbonylative coupling, alkoxy carbonylation, thio carbonylation, and amino carbonylation. This review meticulously examines the mechanistic aspects of how magnetic fields influenced catalytic performance between 2014 and the end of 2024.

Fig. 1. Advantages of transition metals for catalysis.

Fig. 2. Advantages of catalysis based on magnetic separation.

Fig. 3. Preparation of magnetic nanoparticles.

Fig. 4. Characterization of magnetic catalysts.

Fig. 5. MNP-supported transition metals for catalysis in carbonylation reactions.

Fig. 6. Structure of magnetically reusable catalysts (MRC-1–5).

Scheme 1. Scope of the ImmPd(0)–MNPs catalyst [MRC-1] for a one-pot three-component carbonylative Suzuki–Miyaura coupling reaction of aryl iodides with aryl boronic acid and Mo(CO)₆.

Scheme 2. Scope of the Fe₃O₄@SiO₂–SH–Pd^II catalyst [MRC-2] for the one-pot, three-component carbonylative Suzuki coupling reactions of aryl iodides, aryl boronic acids, and carbon monoxide.

Scheme 3. Scope of the Fe₃O₄/PPy–Pd(ii) catalyst [MRC-3] for one-pot, three-component carbonylative Suzuki coupling reactions of aryl iodides, aryl boronic acids, and carbon monoxide.

Scheme 4. Scope of the Fe₃O₄–bis(Py-imine)–PdCl₂ catalyst [MRC-4] for one-pot, three-component carbonylative Suzuki coupling reactions of aryl iodides, aryl boronic acids, and Mo(CO)₆.

Scheme 5. Scope of the Fe₃O₄@SiO₂–2P–PdCl₂ catalyst [MRC-5] for one-pot, three-component carbonylative Suzuki coupling reactions of aryl iodides, aryl boronic acids, and HCCOH as the carbonyl source.

Fig. 7. Structure of magnetically reusable catalysts (MRC-6–12).

Scheme 6. Scope of the Fe₃O₄@arginine–Pd(0) catalyst [MRC-6] for one-pot, three-component carbonylative Suzuki coupling reactions of aryl iodides, aryl boronic acids, and Cr(CO)₆ as the carbonyl source.

Scheme 7. Scope of the Fe₃O₄@DopPy–Pd(0) catalyst [MRC-7] for one-pot, three-component carbonylative Suzuki coupling reactions of aryl iodides, aryl boronic acids, and Mo(CO)₆ as the carbonyl source.

Scheme 8. Scope of the Fe₃O₄@DH/Ph–ImH–Phen–Pd(0) catalyst [MRC-8] for one-pot, three-component carbonylative Suzuki coupling reactions of aryl iodides, aryl boronic acids, and Cr(CO)₆ as the carbonyl source.

Scheme 9. Scope of the Fe₃O₄@AMBA–BiPy–Pd(0) catalyst [MRC-9] for one-pot, three-component carbonylative annulation reactions of 2-iodophenol derivatives, terminal alkynes, and Cr(CO)₆.

Scheme 10. Scope of the Fe₃O₄@AFPA–Pd(0) catalyst [MRC-10] for one-pot, three-component carbonylative annulation reactions of 2-iodophenol derivatives, terminal alkynes, and Mn(CO)₃.

Scheme 11. Scope of the Fe₃O₄@SiO₂–Diol–Phen–Pd(0) catalyst [MRC-13] for the synthesis of quinoline-4(1H)-one derivatives via one-pot, three-component carbonylative reactions.

Scheme 12. Scope of the Fe₃O₄@BA/Pyrim–carboxamide–NiCl₂ catalyst [MRC-14] for one-pot, three-component carbonylative annulation reactions of aryl iodides with aryl or benzyl phenols or thiols, and Cr(CO)₆.

Fig. 8. Structure of magnetically reusable catalysts (MRC-13–15).

Scheme 13. Scope of the Fe₃O₄@benzo[d]imidazole–Zr catalyst [MRC-12] for the synthesis of thioester derivatives via one-pot, three-component thiocarbonylation reactions.

Scheme 14. Scope of the rGO/Fe₃O₄–CuO catalyst [MRC-15] for one-pot, three-component thioesterification annulation reactions.

Scheme 15. Scope of the Pd/Fe₃O₄ catalyst [MRC-16] for one-pot, three-component esterification annulation reactions.

Scheme 16. Scope of the MNPs–Acac@Cu catalyst [MRC-11] for the synthesis of thioester derivatives via one-pot, three-component thiocarbonylation reactions.

Scheme 17. Scope of the MNP–Im–NH₂–Pd catalyst [MRC-16] for one-pot, three-component esterification and amino carbonylation annulation reactions.

Fig. 9. Structure of magnetically reusable catalysts (MRC-15–17).

Scheme 18. Scope of the Fe₃O₄@APPA–Pd catalyst [MRC-17] for one-pot, three-component esterification annulation reactions.

Scheme 19. Scope of the Fe₃O₄@APPA–Pd catalyst [MRC-17] for one-pot, three-component amino carbonylation annulation reactions.

Scheme 20. Scope of the MNPs–dopamine–BiPy–Pd(0) catalyst [MRC-16] for one-pot, three-component amino carbonylation annulation reactions.

Scheme 21. Scope of the Fe₃O₄@SiO₂–Phen–Pd(0) catalyst [MRC-19] for one-pot, three-component amino carbonylation annulation reactions of 2-aminobenzothiazoles.

Mosstafa Kazemi

Ramin Javahershenas