Citation: Wang Huaran, Tang Yu, Yang Jun, Zhang Yuanming. A Simple and Efficient Synthesis of Tertiary Alcohols via Ta₂O₅- Catalyzed Barbier-Grignard Addition of Unactivated Aryl Bromides to Aryl Acids[J]. Chinese Journal of Organic Chemistry, ;2016, 36(10): 2456-2462. doi: 10.6023/cjoc201602025 shu

A Simple and Efficient Synthesis of Tertiary Alcohols via Ta₂O₅- Catalyzed Barbier-Grignard Addition of Unactivated Aryl Bromides to Aryl Acids

1.
Department of Chemistry, Jinan University, Guangzhou 510632

Corresponding author: Tang Yu, tytang@jnu.edu.cn Zhang Yuanming, tzhangym@jnu.edu.cn
Received Date: 24 February 2016
Revised Date: 3 May 2016

Fund Project: Project supported by the National Natural Science Foundation of China No.21276104

Figures(2)

Carried out in THF-toluene at 103℃, the first one-pot Barbier-Grignard reaction to synthesize tertiary alcohols has been developed and systematically investigated using aromatic acids and unactivated aryl bromides in the presence of 10 mol% of Ta₂O₅. A wide range of substituted tertiary alcohols were obtained in moderate to good yields of 48%~87%. Steric and electronic effects of reactants on the reaction have been discussed. A possible mechanism catalyzed by Ta₂O₅ is proposed.
- aryl acid,
- barbier-grignard-type reaction,
- synthesis,
- tertiary alcohol
1. [1]
2. [2]
  Li, C.-J. Chem. Rev. 2005105, 3095.
3. [3]
  Knochel, P.; Dohle, W.; Gommermann, N.; Kneisel, F. F.; Kopp, F.; Korn, T.; Sapountzis, I. Angew. Chem., Int. Ed. 2003, 42, 4302. (b) Silverman, G. S.; Rakita, P. E. Handbook of Grignard Reagents, CRC Press, New York, 1996. (c) Richey, H. G. Grignard Reagents:New Developments, John Wiley & Sons Inc, New York, 2000.
4. [4]
  Wakefield, B. J.; Salford, U. O. Organomagnesium Methods in Organic Chemistry, Academic Press, New York, 1995.
5. [5]
  Li, C.-J. Tetrahedron 1996, 52, 5643. (b) Li, C.-J.; C.T.-H. Tetrahedron 1999, 55, 11149.
6. [6]
  Kashyap, B.; Phukan, P. Tetrahedron Lett. 2013, 54, 6324. (b) Augé, J.; Lubin-Germain, N.; Thiaw-Woaye, A. Tetrahedron Lett. 1999, 40, 9245. (c) Li, C.-J.; Zhang, W.-C. J. Am. Chem. Soc. 1998, 120, 9102. (d) Keh, C. C. K.; Wei, C.-M.; Li, C.-J. J. Am. Chem. Soc. 2003, 125, 4062. (e) Hirayama, L. C.; Haddad, T. D.; Oliver, A. G.; Singaram, B. J. Org. Chem. 2012, 77, 4342. (f) Munoz-Bascon, J.; Sancho-Sanz, I.; Alvarez-Manzaneda, E.; Rosales, A.; Oltra, J. E. Chemistry 2012, 18, 14479.
7. [7]
  Oudeyer, S.; Léonel, E.; Paugam, J. P.; Nédélec, J.-Y. Tetrahedron 2014, 70, 919. (b) Scala, A. D.; Garbacia, S.; Helion, F.; Lannou, M. I.; Namy, J. L. Eur. J. Org. Chem. 2002, 2989. (c) Chouhan, M.; Sharma, R.; Nair, V. A. Appl. Organomet. Chem. 2011, 25, 470. (d) Wen, Y.-M.; Chen, G.-F.; Huang, S.-Q.; Tang, Y.; Yang, J.; Zhang, Y.-M. Adv. Synth. Catal. 2016, 358, 947.
8. [8]
  Shen, Z.-L.; Loh, T. P. Org. Lett. 2007, 9, 5413. (b) Lombardo, M.; Morganti, S.; Trombini, C. J. Org. Chem. 2003, 68, 997.
9. [9]
  Zhou, F.; Li, C.-J. Nat. Commun. 2014, 5, 4254.
10. [10]
11. [11]
  Marie-Isabelle L.; Hélion, F.; Namy, J. L. Tetrahedron Lett. 2002, 43, 8007. (b) Gao, F.; Deng, X.-J.; Tang, Y.; Tang, J.-P.; Yang, J.; Zhang, Y.-M. Tetrahedron Lett. 2014, 55, 880.
12. [12]
  Dishart, K. T.; Levin, R. J. Am. Chem. Soc. 1956, 78, 2268.
13. [13]
  Watanabe, S.; Suga, K.; Fujita, T.; Saito, N. Aust. J. Chem. 1977, 30, 427.
14. [14]
  Fiandanese, V.; Marchese, G.; Ronzini, L. Tetrahedron Lett. 1983, 24, 3677.
15. [15]
  Watanabe, S.; Suga, K.; Yamaguchi, Y. J. Chem. Technol. Biotechnol. 1972, 22, 43.
16. [16]
17. [17]
  Eisch, J. J.; Liu, W.; Zhu, L.; Rheingold, A. L. Eur. J. Org. Chem. 2015, 7384.
18. [18]
  Good, J. A.; Wang, F.; Rath, O.; Kaan, H. Y. K.; Talapatra, S. K.; Podgórski, D.; Kozielski, F. J. Med. Chem 2013, 56, 1878.
19. [19]
  Hatano, T.; Kato, T. Tetrahedron 2008, 64, 8368.
20. [20]
  Chen, C.; Yang, Y.; Xi, F. J. Polym. Sci., Part A:Polym. Chem. 2001, 39, 430.
21. [21]
  Bodendiek, S. B.; Rubinos, C.; Trelles, M. P.; Coleman, N.; Jenkins, D. P.; Wulff, H.; Srinivas, M. Front. Pharmacol. 2012, 3, 106.
22. [22]
  Teng, M.-Y.; Liu, Y.; Li, S.-L.; Huang, G.-L.; Jiang, J.-L.; Wang, L.-Y. RSC Adv. 2013, 3, 9016.
23. [23]
  Horn, M.; Mayr, H. Eur. J. Org. Chem. 2011, 2011, 6470.
24. [24]
  Ueura, K.; Miyamura, S.; Satoh, T.; Miura, M. J. Organomet. Chem. 2006, 691, 2821.
25. [25]
  Weber, E.; Skobridis, K.; Wierig, A.; Goldberg, I. J. Incl. Phenom. Mol. Recognit. Chem. 1997, 28, 163.
26. [26]
  Abarca, B.; Asensio, G.; Ballesteros, R.; Varea, T. J. Org. Chem. 1991, 56, 3224.
27. [27]
  Bai, J.-C.; Zhou, W.-K.; Ding, H.-X. J. Organomet. Chem. 1989, 367, C9.
28. [28]
  Evans, A. G.; Jones, J.; Osborne, G. Trans. Faraday Soc. 1954, 50, 16.
29. [29]
  Wang, F.; Good, J. A.; Rath, O.; Kaan, H. Y. K.; Sutcliffe, O. B.; Mackay, S. P.; Kozielski, F. J. Med. Chem. 2012, 55, 1511.
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A Simple and Efficient Synthesis of Tertiary Alcohols via Ta2O5- Catalyzed Barbier-Grignard Addition of Unactivated Aryl Bromides to Aryl Acids

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通讯作者: 陈斌, bchen63@163.com

A Simple and Efficient Synthesis of Tertiary Alcohols via Ta₂O₅- Catalyzed Barbier-Grignard Addition of Unactivated Aryl Bromides to Aryl Acids