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
1. [1]
  Haofan Niu , Yuhan Wu , Xinran Li , Longmei Li , Dong Wang , Yongce Zhang , Fengyu Liu , Wei Bai . 自驱动固体酸催化乙酸苄酯的合成. University Chemistry, 2026, 41(1): 1-8. doi: 10.12461/PKU.DXHX202505049
2. [2]
  Shuting KONG , Fengshi ZHANG , Zhiyi LU , Yanling LIU , Minglang YE , Zhengfang HU , Longsheng WANG , Bing HU , Haiying WANG . Research advance of the preparation of tributyl citrate catalyzed by supported heteropolyacid catalysts. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 441-452. doi: 10.11862/CJIC.20250303
3. [3]
  Xiaofei Liu , He Wang , Li Tao , Weimin Ren , Xiaobing Lu , Wenzhen Zhang . Electrocarboxylation of Benzylic Phosphates and Phosphinates with Carbon Dioxide. Acta Physico-Chimica Sinica, 2024, 40(9): 2307008-0. doi: 10.3866/PKU.WHXB202307008
4. [4]
  Yifeng TAN , Ping CAO , Kai MA , Jingtong LI , Yuheng WANG . Synthesis of pentaerythritol tetra(2-ethylthylhexoate) catalyzed by h-MoO₃/SiO₂. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2155-2162. doi: 10.11862/CJIC.20240147
5. [5]
  Wei LI , Jianjie XU , Linlin WANG , Chuanbing HOU , Hongliang HAN , Qionghua JIN . Synthesis, structure, and photocatalytic properties of {PMo₁₂}-based rare-earth tetraisopropyl ethylenediphosphonate complexes. Chinese Journal of Inorganic Chemistry, 2026, 42(10): 2077-2091. doi: 10.11862/CJIC.20260220
6. [6]
  Haoyu Sun , Dun Li , Yuanyuan Min , Yingying Wang , Yanyun Ma , Yiqun Zheng , Hongwen Huang . Hierarchical Palladium-Copper-Silver Porous Nanoflowers as Efficient Electrocatalysts for CO₂ Reduction to C₂₊ Products. Acta Physico-Chimica Sinica, 2024, 40(6): 2307007-0. doi: 10.3866/PKU.WHXB202307007
7. [7]
  Zixuan Zhao , Miao Fan . “Carbon” with No “Ester”: A Boundless Journey of CO₂ Transformation. University Chemistry, 2025, 40(7): 213-217. doi: 10.12461/PKU.DXHX202409040
8. [8]
  Shiyi Chen , Jialong Fu , Jianping Qiu , Guoju Chang , Shiyou Hao . Waste medical mask-derived carbon quantum dots enhance the photocatalytic degradation of polyethylene terephthalate (PET) over BiOBr/g-C₃N₄ S-scheme heterojunction. Acta Physico-Chimica Sinica, 2026, 42(1): 100135-0. doi: 10.1016/j.actphy.2025.100135
9. [9]
  Ping Song , Nan Zhang , Jie Wang , Rui Yan , Zhiqiang Wang , Yingxue Jin . Experimental Teaching Design on Synthesis and Antitumor Activity Study of Cu-Pyropheophorbide-a Methyl Ester. University Chemistry, 2024, 39(6): 278-286. doi: 10.3866/PKU.DXHX202310087
10. [10]
  Jiayi Yang , Jianxiu Hao , Huacong Zhou , Quansheng Liu . “Gorgeous Transformation” of Carbon Dioxide into Cyclic Carbonates: Catalyst Types and Roles. University Chemistry, 2026, 41(2): 178-189. doi: 10.12461/PKU.DXHX202502105
11. [11]
  Lirui Shen , Kun Liu , Ying Yang , Dongwan Li , Wengui Chang . Synthesis and Application of Decanedioic Acid-N-Hydroxysuccinimide Ester: Exploration of Teaching Reform in Comprehensive Applied Chemistry Experiment. University Chemistry, 2024, 39(8): 212-220. doi: 10.3866/PKU.DXHX202312035
12. [12]
  Jinghua Wang , Yanxin Yu , Yanbiao Ren , Yesheng Wang . Integration of Science and Education: Investigation of Tributyl Citrate Synthesis under the Promotion of Hydrate Molten Salts for Research and Innovation Training. University Chemistry, 2024, 39(11): 232-240. doi: 10.3866/PKU.DXHX202402057
13. [13]
  Yu Peng , Jiawei Chen , Yue Yin , Yongjie Cao , Mochou Liao , Congxiao Wang , Xiaoli Dong , Yongyao Xia . Tailored cathode electrolyte interphase via ethylene carbonate-free electrolytes enabling stable and wide-temperature operation of high-voltage LiCoO₂. Acta Physico-Chimica Sinica, 2025, 41(8): 100087-0. doi: 10.1016/j.actphy.2025.100087
14. [14]
  Yajin Li , Huimin Liu , Lan Ma , Jiaxiong Liu , Dehua He . Photothermal Synthesis of Glycerol Carbonate via Glycerol Carbonylation with CO₂ over Au/Co₃O₄-ZnO Catalyst. Acta Physico-Chimica Sinica, 2024, 40(9): 2308005-0. doi: 10.3866/PKU.WHXB202308005
15. [15]
  Ke Li , Chuang Liu , Jingping Li , Guohong Wang , Kai Wang . Architecting Inorganic/Organic S-Scheme Heterojunction of Bi₄Ti₃O₁₂ Coupling with g-C₃N₄ for Photocatalytic H₂O₂ Production from Pure Water. Acta Physico-Chimica Sinica, 2024, 40(11): 2403009-0. doi: 10.3866/PKU.WHXB202403009
16. [16]
  Yuan Xue , Yanjun Zhang , Jun Du , Zushun Xu , Guangfu Liao , Qing Li . Introducing dual-functional site on carbon nitride: steering carrier migration and O₂ activation for boosted H₂O₂ photosynthesis. Acta Physico-Chimica Sinica, 2026, 42(9): 100311-0. doi: 10.1016/j.actphy.2026.100311
17. [17]
  Ran Yu , Chen Hu , Ruili Guo , Ruonan Liu , Lixing Xia , Cenyu Yang , Jianglan Shui . Catalytic Effect of H₃PW₁₂O₄₀ on Hydrogen Storage of MgH₂. Acta Physico-Chimica Sinica, 2025, 41(1): 100001-0. doi: 10.3866/PKU.WHXB202308032
18. [18]
  Fan Fan , Hao Xiu , Yuting Wang , Yongpeng Cui , Yajun Wang . Construction of NH₂-MIL-125/Na-doped g-C₃N₄ composite S-scheme heterojunction and its performance in photocatalytic hydrogen peroxide production. Acta Physico-Chimica Sinica, 2026, 42(2): 100143-0. doi: 10.1016/j.actphy.2025.100143
19. [19]
  Ling Liu , Haibin Wang , Genrong Qiang . Curriculum Ideological and Political Design for the Comprehensive Preparation Experiment of Ethyl Benzoate Synthesized from Benzyl Alcohol. University Chemistry, 2024, 39(2): 94-98. doi: 10.3866/PKU.DXHX202304080
20. [20]
  Shuying Zhu , Shuting Wu , Ou Zheng . Improvement and Expansion of the Experiment for Determining the Rate Constant of the Saponification Reaction of Ethyl Acetate. University Chemistry, 2024, 39(4): 107-113. doi: 10.3866/PKU.DXHX202310117

Get Citation

PDF

XML

Metrics

PDF Downloads(12)
Abstract views(3117)
HTML views(376)

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

Metrics

通讯作者: 陈斌, bchen63@163.com

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