Abstract
Pd-catalyzed decarboxylative cross-couplings of 2-(2-azaaryl)acetates with aryl halides and triflates have been discovered. This reaction is potentially useful for the synthesis of some functionalized pyridines, quinolines, pyrazines, benzoxazoles, and benzothiazoles. Theoretical analysis shows that the nitrogen atom at the 2-position of the heteroaromatics directly coordinates to Pd(II) in the decarboxylation transition state.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
(a) Baudoin, O. (2007). Angewandte Chemie International Edition, 46, 1373–1375. (b) Goossen, L. J., Rodriguez, N., & Goossen, K. (2008). Angewandte Chemie International Edition, 47, 3100–3120.
(a) Myers, A. G., Tanaka, D., & Mannion, M. R. (2002). Journal of the American Chemical Society, 124, 11250–11251. (b) Tanaka, D., & Myers, A. G. (2004). Organic Letters, 6, 433–436. (c) Tanaka, D., Romeril, S. P., & Myers, A. G. (2005). Journal of the American Chemical Society, 127, 10323–10333.
(a) Forgione, P., Brochu, M. C., St-Onge, M., Thesen, K. H., Bailey, M. D., & Bilodeau, F. (2006). Journal of the American Chemical Society, 128, 11350–11363. (b) Bilodeau F., Brochu, M. C., Guimond N., Thesen K. H., & Forgione P. (2010). The Journal of Organic Chemistry, 75, 1550–1560.
(a) Becht, J.-M., & Le Drian, C. (2008). Organic Letters, 10, 3161–3164. (b) Becht, J.-M., Catala, C., Le Drian, C., & Wagner, A. (2007). Organic Letters, 9, 1781–1783.
(a) Maehara, A., Tsurugi, H., Satoh, T., & Miura, M. (2008). Organic Letters, 10, 1159–1162. (b) Yamashita, M., Hirano, K., Satoh, T., & Miura, M. (2009). Organic Letters, 11, 2337–2340.
(a) Moon, J., Jeong, M., Nam, H., Ju, J., Moon, J. H., Jung, H. M., & Lee, S. (2008). Organic Letters, 10, 945–948. (b) Moon, J., Jang, M., & Lee, S. (2009). The Journal of Organic Chemistry, 74, 1403–1406.
(a) Wang, Z. Y., Ding, Q. P., He, X. D., & Wu, J. (2009). Tetrahedron, 65, 4635–4638. (b) Voutchkova, A., Coplin, A., Leadbeater, N. E., & Crabtree, R. H. (2008). Chemical Communications, 6312–6314. (c) Wang, C., Piel, I., & Glorius, F. (2009). Journal of the American Chemical Society, 131, 4194–4195.
(a) Shang, R., Fu, Y., Li, J. B., Zhang, S. L., Guo, Q. X., & Liu, L. (2009). Journal of the American Chemical Society, 131, 5738–5739. (b) Shang, R., Xu, Q., Jiang, Y.-Y., Wang, Y., & Liu, L. (2010). Organic Letters, 12, 1000–1003.
(a) Goossen, L. J., Deng, G., & Levy, L. M. (2006). Science, 313, 662–664. (b) Goossen, L. J., Rodriguez, N., Melzer, B., Linder, C., Deng, G., & Levy, L. M. (2007). Journal of the American Chemical Society, 129, 4824–4833. (c) Goossen, L. J., & Melzer, B. (2007). The Journal of Organic Chemistry, 72, 7473–7476. (d) Goossen, L. J., Zimmermann, B., & Knauber, T. (2008). Angewandte Chemie International Edition, 47, 7103–7106. (e) Goossen, L. J., & Knauber, T. (2008). The Journal of Organic Chemistry, 73, 8631–8634. (f) Goossen, L. J., Rodriguez, N., & Linder, C. (2008). Journal of the American Chemical Society, 130, 15248–15249. (g) Goossen, L. J., Manojolinho, F., Khan, B. A., & Rodriguez, N. (2009). The Journal of Organic Chemistry, 74, 2620–2623. (h) Goossen, L. J., Rudolphi, F., Oppel, C., & Rodriguez, N. (2008). Angewandte Chemie International Edition, 47, 3043–3045. (i) Goossen, L. J., Rodriguez, N., Lange P., & Linder, C. (2010). Angewandte Chemie International Edition, 49, 1111–1114.
Shang, R., Fu, Y., Wang, Y., Xu, Q., Yu, H.-Z., & Liu, L. (2009). Angewandte Chemie International Edition, 48, 9350–9354.
(a) Burger, E. C., & Tunge, J. A. (2006). Journal of the American Chemical Society, 128, 10002–10003. (b) Waetzig, S. R., & Tunge, J. A. (2007). Journal of the American Chemical Society, 129, 4138–4139. (c) Trost, B. M., Xu, J., & Schmidt, T. (2009). Journal of the American Chemical Society, 131, 18343–18357. (d) Trost, B. M., Xu, J., & Schmidt, T. (2008). Journal of the American Chemical Society, 130, 11852–11853.
Decarboxylation of amino acids has been shown to generate electrophilic species: (a) Bi, H.-P., Zhao, L., Liang, Y.-M., & Li, C.-J. (2009). Angewandte Chemie International Edition, 48, 792–795. (b) Bi, H.-P., Chen, W.-W., Liang, Y.-M., & Li, C.-J. (2009). Organic Letters, 11, 3246–3249. (c) Zhang, C., & Seidel, D. (2010). Journal of the American Chemical Society, 132, 1798–1799.
(a) Niwa, T., Yorimitsu, H., & Oshima, K. (2007). Angewandte Chemie International Edition, 46, 2643–2645. (b) For a related study, see: Qian, B., Guo, S., Shao, J., Zhu, Q., Yang, L., Xia, C., & Huang, H. (2010). Journal of the American Chemical Society, 132, 3650–3651.
2- and 4-Pyridylacetic acids decarboxylate thermally in high yield at 90 °C, while the 3-derivative is stable at that temperature; see: Stermitz, F. R., & Huang, W. H. (1971). Journal of the American Chemical Society, 93, 3427–3431.
Campeau, L. C., Schipper, D. J., & Fagnou, K. (2008). Journal of the American Chemical Society, 130, 3266–3267.
For related theoretical analysis of decarboxylation and decarboxylative coupling of C(sp2)-COOH, see: Zhang, S.-L., Fu, Y., Shang, R., Guo, Q.-X., & Liu, L. (2010). Journal of the American Chemical Society, 132, 638–646.
We isolated the CP2 complex with 4-CN-phenyl substitution according to a previous paper (Yin, J., & Buchwald, S. L. (2002). Journal of the American Chemical Society, 124, 6043–6048). We found that CP2 is catalytically active. By addition of CP2 to the reaction between bromobenzene and potassium 2-(2-pyridyl)acetate, we could obtain the desired product (2-benzylpyridine) in 99% GC yield. We also observed a small amount of crossover byproduct, namely, 4-(pyridin-2-ylmethyl)benzonitrile.
(a) Kawatsura, M., & Hartwig, J. F. (1999). Journal of the American Chemical Society, 121, 1473–1478. (b) Jorgensen, M., Lee, S., Liu, X., Wolkowski, J. P., & Hartwig, J. F. (2002). Journal of the American Chemical Society, 124, 12557–12565. (c) Hama, T., Liu, X., Culkin, D. A., & Hartwig, J. F. (2003). Journal of the American Chemical Society, 125, 11176–11177. (d) Nguyen, H. N., Huang, X., & Buchwald, S. L. (2003). Journal of the American Chemical Society, 125, 11818–11819.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
Copyright information
© 2017 Springer Nature Singapore Pte Ltd.
About this chapter
Cite this chapter
Shang, R. (2017). Construction of C(sp3)–C(sp2) Bonds Via Palladium-Catalyzed Decarboxylative Couplings of 2-(2-Azaaryl)Acetate Salts with Aryl Halides. In: New Carbon–Carbon Coupling Reactions Based on Decarboxylation and Iron-Catalyzed C–H Activation. Springer Theses. Springer, Singapore. https://doi.org/10.1007/978-981-10-3193-9_5
Download citation
DOI: https://doi.org/10.1007/978-981-10-3193-9_5
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-10-3192-2
Online ISBN: 978-981-10-3193-9
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)