Research Article
N-Alkoxycarbonyl / carbamoylmethyl substituted 1H-imidazol-2-yliden-Pd (II) complexes as highly efficient catalysts for Suzuki-Miyaura cross-coupling reaction
Abstract
N-Alkoxycarbonyl / carbamoylmethyl substituted 1H-imidazol-2-yliden-Pd (II) complexes (Cat-1-5) were used for the first time as catalysts in the Suzuki-Miyaura reaction between aryl bromides and arylboronic acids. All complexes screened were found to be excellent catalysts in the selected coupling between 4-bromobenzaldehyde and phenylboronic acid at room temperature. Cat-3 was shown to be the most efficient one and used for the optimisation of the reaction conditions and determining the substrate scope. The application of the optimised method provided a series of biaryls (3a-l) in excellent isolated yields. With these promising results the catalysts could be applied succesfully to some other classic cross-coupling reactions such as Sonogashira, Stille and Buchwald-Hartwig.
Thanks
Prof. Dr. Nejdet Coşkun
References
- [1] Blakemore D.C., Suzuki-Miyaura Coupling. In: Blakemore D.C., Doyle P.M., Fobian Y.M., (Eds). Synthetic Methods in Drug Discovery Volume 1. Cambridge: RSC, (2016); 1-69.
- [2] Koshvandi T. K. A., Heravi M. M., Momeni T., Current Applications of Suzuki–Miyaura Coupling Reaction in The Total Synthesis of Natural Products: An update, Appl. Organomet. Chem., 32(3) (2018) 1–59.
- [3] Dhangar G., Serrano J. L., Schulzke C., Gunturu K. C., Kapdi A. R., Palladacycle-Catalyzed Triple Suzuki Coupling Strategy for the Synthesis of Anthracene-Based OLED Emitters, ACS Omega, 2(7) (2017) 3144–3156.
- [4] García-López J. A., Greaney M. F., Synthesis of biaryls using aryne intermediates, Chem. Soc. Rev., 45(24) (2016) 6766–6798.
- [5] Beletskaya I. P., Alonso F., Tyurin V., The Suzuki-Miyaura reaction after the Nobel prize, Coord. Chem. Rev., 385(2019) 137–173.
- [6] Hooshmand S. E., Heidari B., Sedghi R., Varma R. S., Recent advances in the Suzuki-Miyaura cross-coupling reaction using efficient catalysts in eco-friendly media, Green Chem., 21(3) (2019) 381–405.
- [7] Froese R. D. J., Lombardi C., Pompeo M., Rucker R. P., Organ M. G., Designing Pd-N-Heterocyclic Carbene Complexes for High Reactivity and Selectivity for Cross-Coupling Applications, Acc. Chem. Res., 50(9) (2017) 2244–2253.
- [8] Charra V., de Frémont P., Braunstein P., Multidentate N-heterocyclic carbene complexes of the 3d metals: Synthesis, structure, reactivity and catalysis, Coord. Chem. Rev., 341 (2017) 53–176.
- [9] Korch K. M., Watson D. A., Cross-Coupling of Heteroatomic Electrophiles, Chem. Rev., 119(13) (2019) 8192–8228.
- [10] Peris E., Smart N-Heterocyclic Carbene Ligands in Catalysis, Chem. Rev., 118(19) (2018) 9988–10031.
- [11] Coşkun N., Çetin M., Thermal rearrangements of tetrahydroimidazo[1,5-b]isoxazole-2,3-dicarboxylates. Synthesis of 3H-imidazol-1-ium ylides and their silver derivatives, Tetrahedron, 66(11) (2010) 2053–2060.
- [12] Syntheses of metal heterocyclic carbene enolates as coupling reactions catalysts. Available at: https://patents.google.com/patent/WO2017099693A1/it.
- [13] Çetin Korukçu M., Coşkun N., Synthesis and catalytic activities of 1-alkoxycarbonyl- and 1-carbamoylmethyl-5-phenyl-3-aryl-3H-imidazol-1-yliden-Pd(II) complexes, J. Organomet. Chem., 832(2017) 47–56.
- [14] Simoni D., Giannini G., Roberti M., Rondanin R., Baruchello R., Rossi M., Grisolia G., Invidiata F. P., Aiello S., Marino S., Cavallini S., Siniscalchi A., Gebbia N., Crosta L., Grimaudo S., Abbadessa V., Cristina A. D., Tolomeo M., Studies on the apoptotic activity of natural and synthetic retinoids: Discovery of a new class of synthetic terphenyls that potently support cell growth and inhibit apoptosis in neuronal and HL-60 cells, J. Med. Chem., 48(13) (2005) 4293–4299.
- [15] Du Z., Zhou W., Wang F., Wang J.X., In situ generation of palladium nanoparticles: Ligand-free palladium catalyzed ultrafast Suzuki-Miyaura cross-coupling reaction in aqueous phase at room temperature, Tetrahedron, 67(26) (2011) 4914–4918.
N-Alkoxycarbonyl / carbamoylmethyl substituted 1H-imidazol-2-ylidenPd (II) complexes as highly efficient catalysts for Suzuki-Miyaura crosscoupling reaction
Abstract
N-Alkoxycarbonyl / carbamoylmethyl substituted 1H-imidazol-2-yliden-Pd (II) complexes (Cat-1-5) were used for the first time as catalysts in the Suzuki-Miyaura reaction between aryl bromides and arylboronic acids. All complexes screened were found to be excellent catalysts in the selected coupling between 4-bromobenzaldehyde and phenylboronic acid at room temperature. Cat-3 was shown to be the most efficient one and used for the optimisation of the reaction conditions and determining the substrate scope. The application of the optimised method provided a series of biaryls (3a-l) in excellent isolated yields. With these promising results the catalysts could be applied succesfully to some other classic cross-coupling reactions such as Sonogashira, Stille and Buchwald-Hartwig.
References
- [1] Blakemore D.C., Suzuki-Miyaura Coupling. In: Blakemore D.C., Doyle P.M., Fobian Y.M., (Eds). Synthetic Methods in Drug Discovery Volume 1. Cambridge: RSC, (2016); 1-69.
- [2] Koshvandi T. K. A., Heravi M. M., Momeni T., Current Applications of Suzuki–Miyaura Coupling Reaction in The Total Synthesis of Natural Products: An update, Appl. Organomet. Chem., 32(3) (2018) 1–59.
- [3] Dhangar G., Serrano J. L., Schulzke C., Gunturu K. C., Kapdi A. R., Palladacycle-Catalyzed Triple Suzuki Coupling Strategy for the Synthesis of Anthracene-Based OLED Emitters, ACS Omega, 2(7) (2017) 3144–3156.
- [4] García-López J. A., Greaney M. F., Synthesis of biaryls using aryne intermediates, Chem. Soc. Rev., 45(24) (2016) 6766–6798.
- [5] Beletskaya I. P., Alonso F., Tyurin V., The Suzuki-Miyaura reaction after the Nobel prize, Coord. Chem. Rev., 385(2019) 137–173.
- [6] Hooshmand S. E., Heidari B., Sedghi R., Varma R. S., Recent advances in the Suzuki-Miyaura cross-coupling reaction using efficient catalysts in eco-friendly media, Green Chem., 21(3) (2019) 381–405.
- [7] Froese R. D. J., Lombardi C., Pompeo M., Rucker R. P., Organ M. G., Designing Pd-N-Heterocyclic Carbene Complexes for High Reactivity and Selectivity for Cross-Coupling Applications, Acc. Chem. Res., 50(9) (2017) 2244–2253.
- [8] Charra V., de Frémont P., Braunstein P., Multidentate N-heterocyclic carbene complexes of the 3d metals: Synthesis, structure, reactivity and catalysis, Coord. Chem. Rev., 341 (2017) 53–176.
- [9] Korch K. M., Watson D. A., Cross-Coupling of Heteroatomic Electrophiles, Chem. Rev., 119(13) (2019) 8192–8228.
- [10] Peris E., Smart N-Heterocyclic Carbene Ligands in Catalysis, Chem. Rev., 118(19) (2018) 9988–10031.
- [11] Coşkun N., Çetin M., Thermal rearrangements of tetrahydroimidazo[1,5-b]isoxazole-2,3-dicarboxylates. Synthesis of 3H-imidazol-1-ium ylides and their silver derivatives, Tetrahedron, 66(11) (2010) 2053–2060.
- [12] Syntheses of metal heterocyclic carbene enolates as coupling reactions catalysts. Available at: https://patents.google.com/patent/WO2017099693A1/it.
- [13] Çetin Korukçu M., Coşkun N., Synthesis and catalytic activities of 1-alkoxycarbonyl- and 1-carbamoylmethyl-5-phenyl-3-aryl-3H-imidazol-1-yliden-Pd(II) complexes, J. Organomet. Chem., 832(2017) 47–56.
- [14] Simoni D., Giannini G., Roberti M., Rondanin R., Baruchello R., Rossi M., Grisolia G., Invidiata F. P., Aiello S., Marino S., Cavallini S., Siniscalchi A., Gebbia N., Crosta L., Grimaudo S., Abbadessa V., Cristina A. D., Tolomeo M., Studies on the apoptotic activity of natural and synthetic retinoids: Discovery of a new class of synthetic terphenyls that potently support cell growth and inhibit apoptosis in neuronal and HL-60 cells, J. Med. Chem., 48(13) (2005) 4293–4299.
- [15] Du Z., Zhou W., Wang F., Wang J.X., In situ generation of palladium nanoparticles: Ligand-free palladium catalyzed ultrafast Suzuki-Miyaura cross-coupling reaction in aqueous phase at room temperature, Tetrahedron, 67(26) (2011) 4914–4918.
There are 15 citations in total.
Details
| Primary Language | English |
|---|---|
| Journal Section | Natural Sciences |
| Authors | |
| Publication Date | March 29, 2021 |
| Submission Date | October 10, 2020 |
| Acceptance Date | January 27, 2021 |
| Published in Issue | Year 2021Volume: 42 Issue: 1 |