Recent advances in the application of nano-catalysts for Hiyama cross-coupling reactions

Abstract

This mini-review highlights the recent developments in the field of metal nanoparticle (NP) catalyzed Hiyama cross-coupling reactions. Most of the nanocatalysts outlined here allow convenient and green synthetic pathways for the construction of carbon-carbon bonds in water and fluoride-free conditions. Literature has been surveyed from 2005 to February 2018.

Scheme 1. Hiyama coupling of aryl siloxanes 1 with aryl bromides 2 catalyzed by a Pd NP in water developed by Sarkar.

Fig. 1. Plot of the size of NP as a function of Pd/PEG molar ratio and yield (%) of the coupled product.

Scheme 2. Plausible mechanism for the Pd NPs-catalyzed coupling of aryl siloxanes 1 with aryl bromides 2 in water.

Fig. 2. Comparison of the catalytic activity of several commercially available Pd/charcoal catalysts in Hiyama cross-coupling reaction of trimethoxyphenylsilane 4 with 3-bromotoluene 5.

Fig. 3. Schematic illustrations of the synthesis for Pd-NP/MWCNT.

Scheme 3. Pd-NPs@XAD-4 catalyzed coupling of trimethoxyphenylsilane 4 with aryl bromides/chlorides 7 reported by Shah and Kaur.

Fig. 4. Synthesis of Pd[CN-bmim]PF₆ (10) by heating of Pd(OAc)₂ with [CN-bmim]PF₆ (9) in MeCN.

Scheme 4. (a) Jain's synthesis of biaryls 13; (b) mechanistic proposal for the formation of biaryls 13.

Scheme 5. Pd@TMS-SBA-15 catalyzed Hiyama coupling of triethoxyphenylsilanes 14 with aryl halides 15.

Scheme 6. Pd(0)-PVP NPs catalyzed synthesis of biaryls 13 reported by Kaur.

Scheme 7. Carbon–carbon cross-coupling reaction between aryl trimethoxysilanes 19 with aryl bromides 20 using Ps-PDONPs as catalyst in water.

Scheme 8. Mechanistic proposal for the reaction in Scheme 7.

Scheme 9. Hiyama coupling using magnetically separable Fe₃O₄@PdNPs.

Fig. 5. TEM images of Pd/Fe₃O₄ nanoparticles before (a) and after (b) catalysis observed at 120 kV.

Fig. 6. Schematic illustration of the preparation of PF-SiO₂@Fe₃O₄–Pd(OAc)₂.

Scheme 10. C–C cross-coupling of phenyltrimethoxysilane 4 with aryl halides 25 catalyzed by PF-SiO₂@Fe₃O₄–Pd(OAc)₂.

Fig. 7. Chemical structure of Fe₃O₄@SiO₂/APTMS/Pd(cdha)₂.

Scheme 11. Synthesis of functionalized biaryls 28 through Pd/ZnO NPs-catalyzed reaction of phenyl trimethoxysilane 4 and aryl halides 27 in ethyleneglycol.

Scheme 12. Synthesis route for the preparation of Pd@DCA-MCM.

Scheme 13. (Pd@DCA-MCM)-catalyzed coupling of triethoxy(phenyl)silane 14 and aryl halides 29.

Fig. 8. Kandathil's synthesis of Pd NPs.

Scheme 14. Pd NPs-catalyzed Hiyama cross-coupling of phenyl trimethoxysilane 4 and aryl halides 31.

Scheme 15. Au-NPs@XAD-4 catalyzed synthesis of biaryls 34 from phenyl trimethoxysilane 4 and aryl halides 33.

Fig. 9. Synthesis route of TF-SiO₂@Fe₃O₄–Ni.

Scheme 16. TF-SiO₂@Fe₃O₄–Ni catalyzed synthesis of biaryls 36 in H₂O/EtOH.

Scheme 17. Palladium-coated nickel nanoclusters catalyzed synthesis of biaryls 38 reported by Pachón.

Scheme 18. Synthesis of styrenes 43via PdNPs-catalyzed coupling of triethoxyvinylsilane 41 with corresponding aryl halides 42.

Scheme 19. PdNPs-catalyzed synthesis of styrenes 45 reported by Planellas.

Scheme 20. Synthesis of symmetrical trans-stilbenes 47via Pd NPs-catalyzed sequential Hiyama–Heck reaction of triethoxyvinylsilane 41 with aromatic diazonium salts 46.

Scheme 21. Plausible mechanism for Pd-NPs-catalyzed sequential Hiyama–Heck reaction.

Scheme 22. PdNPs-catalyzed cross-coupling reaction of aryl and vinyl siloxanes 48 with allyl acetates 49 developed by Ranu.

Scheme 23. Synthesis of diarylmethanes 53via PdNPs-catalyzed Hiyama coupling of aryl siloxanes 51 with benzyl halides 52.

Scheme 24. PdNPs-catalyzed carboxylative coupling of trimethoxyallylsilane 54 with chloromethyl(heter)oarenes 55 reported by Song et al.

Aazam Monfared

Robab Mohammadi

Sheida Ahmadi

Mohammad Nikpassand

Akram Hosseinian