Citation: Duanmu Dandan, Leong Pak-kin, Jiang Qibai, Yan Hong. Pd(Ⅱ)-Catalyzed Synthesis of Benzyl Benzoates via Benzyl C(sp³)-H Activation[J]. Chinese Journal of Organic Chemistry, ;2017, 37(10): 2669-2677. doi: 10.6023/cjoc201704040 shu

Pd(Ⅱ)-Catalyzed Synthesis of Benzyl Benzoates via Benzyl C(sp³)-H Activation

a.
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093
b.
Jiangsu Yangnong Chemical Co., Ltd., Yangzhou 225009

Corresponding author: Jiang Qibai, jiangqibai@163.com Yan Hong, hyan1965@nju.edu.cn
Received Date: 24 April 2017
Revised Date: 22 June 2017
Available Online: 4 October 2017
Fund Project: the National Basic Research Program of China 2013CB922101the National Natural Science Foundation of China 21271102the National Natural Science Foundation of China 21472086Project supported by the National Basic Research Program of China (No. 2013CB922101) and the National Natural Science Foundation of China (Nos. 21271102, 21472086)

Figures(4)

An efficient Pd(Ⅱ)-catalyzed synthesis of benzyl benzoates via direct functionalization of benzyl C(sp³)-H bonds was developed. The method features a broad substrate scope. This method features high tolerance of functional groups, mild reaction condition, and high chemoselective when there are multiple active C(sp³)-H bonds. A plausible oxidative coupling mechanism was proposed on the basis of mechanistic studies.
- Pd(Ⅱ)-catalysis,
- C—H activation,
- benzyl benzoates,
- perester
1. [1]
  Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147. doi: 10.1021/cr900184e
2. [2]
3. [3]
4. [4]
5. [5]
6. [6]
  Li, H.; Li, B.-J.; Shi, Z.-J. Catal. Sci. Technol. 2011, 1, 191. doi: 10.1039/c0cy00076k
7. [7]
  (a) Chen, H.; Cai, C.; Liu, X.; Li, X.; Jiang, H. Chem. Commun. 2011, 47, 12224.
  (b) Liu, W. B.; Zheng, C.; Zhuo, C. X.; Dai, L. X.; You, S. L. J. Am. Chem. Soc. 2012, 134, 4812.
  (c) Li, Q.; Yu, Z. X. Organometallics 2012, 31, 5185.
8. [8]
  Rakshit, S.; Patureau, F. W.; Glorius, F. J. Am. Chem. Soc. 2010, 132, 9585. doi: 10.1021/ja104305s
9. [9]
  (a) Kharasch, M. S.; Fono, A. J. Org. Chem. 1958, 23, 324.
  (b) Kharasch, M. S.; Sosnovsky, G.; Yang, N. C. J. Am. Chem. Soc. 1959, 81, 5819.
  (c) Andrus, M. B.; Lashley, J. C. Tetrahedron 2002, 58, 845.
  (d) Eames, J.; Watkinson, M. Angew. Chem., Int. Ed. 2001, 40, 3567.
  (e) Malkov, A. V.; Bella, M.; Langer, V.; Kocovsky, P. Org. Lett. 2000, 2, 3047.
  (f) Andrus, M. B.; Zhou, Z. J. Am. Chem. Soc. 2002, 124, 8806.
  (g) Rispens, M. T.; Zondercu, C.; Feringa, B. L. Tetrahedron:Asymmetry 1995, 6, 661.
10. [10]
  (a) Dick, A. R.; Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc. 2004, 126, 2300.
  (b) Takahara, S.; Kitamura, A.; Sakuragi, H.; Tokumaru, K. Chem. Lett. 1983, 8, 1315.
11. [11]
  (a) Li, Z.; Cao, L.; Li, C. J. Angew. Chem., Int. Ed. 2007, 46, 6505.
  (b) Pan, S.; Liu, J.; Li, Y.; Li Z. P. Chin. Sci. Bull. 2012, 57, 2382.
  (c) Xiong, T.; Li, Y.; Bi, X.; Lv, Y.; Zhang, Q. Angew. Chem., Int. Ed. 2011, 50, 7140.
12. [12]
  Chen, C.; Xu, X.; Yang, B.; Qing, F. Org. Lett. 2014, 16, 3372. doi: 10.1021/ol501400u
13. [13]
  (a) Weaver, J. D.; Recio, A.; Grenning, A. J.; Tunge, J. A. Chem. Rev. 2011, 111, 1846.
  (b) Kuwano, R. Synthesis 2009, 1049.
14. [14]
  (a) Evangelisti, C.; Schiavi, E.; Aronica, L. A.; Caporusso, A. M.; Vitulli, G.; Bertinietti, L.; Martra, G.; Balerna, A.; Mobilo, S. J. Catal. 2012, 286, 224.
  (b) Zhang, M. J.; Vedantham, P.; Flynn, D. L.; Hanson, P. R. J. Org. Chem. 2004, 69, 8340.
15. [15]
  (a) Jovanovic, J.; Hengeveld, W.; Rebrov, E. V.; Nijhuis, T. A.; Hessel, V.; Schouten, J. C. Chem. Eng. Technol. 2011, 34, 1691.
  (b) Gathirwa, J. W.; Maki, T. Tetrahedron 2012, 68, 370.
  (c) Gok, Y. Alici, B.; Cetinkaya, E.; Ozdemir, I.; Ozeroglu, O.; Turk. J. Chem. 2010, 34, 187.
16. [16]
  Werner, T.; Barrett, A. G. M. J. Org. Chem. 2006, 71, 4302. doi: 10.1021/jo060562m
17. [17]
  (a) Hao, W. Y.; Sha, J. C.; Sheng, S. R.; Cai, M. Z. Catal. Commun. 2008, 10, 257.
  (b) Salvadori, J.; Balducci, E.; Zara, S. Petricci, E.; Taddei, M. J. Org. Chem. 2010, 75, 1841.
  (c) Ramesh, C.; Nakamura, R.; Kubota, Y.; Miwa, M.; Sugi, Y. Synthesis 2003, 4, 501.
18. [18]
  Su, X.-B.; Zhang, Q.-H.; Wu, Y.-Q.; Xu, J.-X. Chin. J. Org. Chem. 2002, 22, 496(in Chinese). doi: 10.3321/j.issn:0253-2786.2002.07.006
19. [19]
  Wu, T.; Mu, X.; Liu, G. Angew. Chem., Int. Ed. 2011, 50, 12578. doi: 10.1002/anie.201104575
20. [20]
  Wei, W.; Zhang, C.; Xu, Y.; Wan, X. Chem. Commun. 2011, 47, 10827. doi: 10.1039/c1cc14602e
21. [21]
  Liu, H.; Shi, G.; Pan, S.; Jiang, Y.; Zhang, Y. Org. Lett. 2013, 15, 4098. doi: 10.1021/ol401687f
22. [22]
  Sather, A. C.; Berryman, O. B.; Ajami, D.; Rebek, Jr. J. Tet-rahedron Lett. 2011, 52, 2100. doi: 10.1016/j.tetlet.2010.11.030
23. [23]
  Khan, K. M.; Maharvi, G. M.; Hayat, S.; Zia, U.; Choudhary, M. I.; Rahman, A. Tetrahedron 2003, 59, 5549. doi: 10.1016/S0040-4020(03)00812-3
24. [24]
  Shen, H.; Lu, X.; Jiang, K.; Yang, K.; Lu, Y.; Zheng, Z.; Lai, G.; Xu, L. Tetrahedron 2012, 68, 8916. doi: 10.1016/j.tet.2012.08.024
25. [25]
  Green, R. A.; Pletcher, D.; Leach, S. G.; Brown, R. C. D. Org. Lett. 2015, 17, 3290. doi: 10.1021/acs.orglett.5b01459
26. [26]
  Blaser, H.; Diggelmann, M.; Meier, H.; Naud, F.; Scheppach, E.; Schnyde, A.; Studer, M. J. Org. Chem. 2003, 68, 3725. doi: 10.1021/jo034112v
27. [27]
  Majji, G.; Guin, S.; Gogoi, A.; Rout, S. K.; Patel, B. K. Chem. Commun. 2013, 49, 3031. doi: 10.1039/c3cc40832a
28. [28]
  Curran, S. P.; Connon, S. J. Angew. Chem., Int. Ed. 2012, 51, 10866. doi: 10.1002/anie.v51.43
29. [29]
  Zhang, S.; Luo, F.; Wang, W.; Jia, X.; Hu, M.; Cheng, J. Tetrahedron Lett. 2010, 51, 3317. doi: 10.1016/j.tetlet.2010.04.075
30. [30]
  Tatamidani, H.; Yokota, K.; Kakiuchi, F.; Chatani, N. J. Org. Chem. 2004, 69, 5615. doi: 10.1021/jo0492719
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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Pd(Ⅱ)-Catalyzed Synthesis of Benzyl Benzoates via Benzyl C(sp3)-H Activation

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通讯作者: 陈斌, bchen63@163.com

Pd(Ⅱ)-Catalyzed Synthesis of Benzyl Benzoates via Benzyl C(sp³)-H Activation