Citation: Fu Xiaopan, Wang Yangyang, Yang Jinyue, Wu Gaorong, Xia Chengcai, Ji Yafei. Fully Substituted Pyrazoles Assisted Palladium-Catalyzed Late-Stage Arylation of C(sp²)—H Bond[J]. Chinese Journal of Organic Chemistry, ;2020, 40(12): 4305-4314. doi: 10.6023/cjoc202005080 shu

Fully Substituted Pyrazoles Assisted Palladium-Catalyzed Late-Stage Arylation of C(sp²)—H Bond

a.
Engineering Research Centre of Pharmaceutical Process Chemistry, Ministry of Education, School of Pharmacy, East China University of Science & Technology, Shanghai 200237
b.
Pharmacy College, Shandong First Medical University & Shandong Academy of Medical Sciences, Taian, Shandong 271016

Corresponding author: Xia Chengcai, xiachc@163.com Ji Yafei, jyf@ecust.edu.cn
Received Date: 28 May 2020
Revised Date: 28 June 2020
Available Online: 22 July 2020
Fund Project: Project supported by the National Natural Science Foundation of China (No. 21676088)the National Natural Science Foundation of China 21676088

Figures(6)

A successful protocol has been developed for palladium-catalyzed late-stage arylation of fully substituted pyrazoles. Through screening of optimazation of reaction parameters, the most efficient reaction conditions for mono-ortho-position arylation were obtained. This reaction features a broad substrate scope, good functional group tolerance as well as good to excellent yield. Moreover, the intermolecular competition experiments and gram scale reaction were also performed. The kinetic isotopic effect (KIE) result reveled C-H bond cleavage was involved in the rate-limiting step and a plausible mechanism was proposed based on the dual-core dimeric palladacycle.
- mono-arylation,
- late-stage functionalization,
- fully substituted pyrazole,
- C(sp²)-H bond
1. [1]
  (a) Giri, R.; Shi, B. F.; Engle, K. M.; Maugel, N.; Yu, J. Q. Chem. Soc. Rev. 2009, 38, 3242.
  (b) Li, B. J.; Shi, Z. J. Chem. Soc. Rev. 2012, 41, 5588.
  (c) Louillat, M. L.; Patureau, F. W. Chem. Soc. Rev. 2014, 43, 901.
  (d) Chen, Z. K.; Wang, B. J.; Zhang, J. T.; Yu, W. L.; Liu, Z. X.; Zhang, Y. H. Org. Chem. Front. 2015, 2, 1107.
  (e) Gensch, T.; James, M. J.; Dalton, T.; Glorius, F. Angew. Chem., Int. Ed. 2018, 57, 2296.
  (f) Li, J. X.; Yang, S. R.; Wu, W. Q.; Jiang, H. F. Eur. J. Org. Chem. 2018, 1284.
  (g) Li, J. X.; Yang, S. R.; Wu, W. Q.; Jiang, H. F. Chem.-Asian J. 2019, 14, 4114.
2. [2]
  (a) Alberico, D.; Scott, M. E.; Lautens, M. Chem. Rev. 2007, 107, 174.
  (b) Seth, K.; Garg, S. K.; Kumar, R.; Purohit, P.; Meena, V. S.; Goyal, R.; Banerjee, U. C.; Chakraborti, A. K. ACS Med. Chem. Lett. 2014, 5, 512.
3. [3]
  (a) Ashenhurst, J. A. Chem. Soc. Rev. 2010, 39, 540.
  (b) Bugaut, X.; Glorius, F. Angew. Chem., Int. Ed. 2011, 50, 7479.
  (c) Cho, S. H.; Kim, J. Y.; Kwak, J.; Chang, S. Chem. Soc. Rev. 2011, 40, 5068.
  (d) Li, B.; Shi, Z. Chem. Soc. Rev. 2012, 41, 5588.
4. [4]
  (a) Li, R.; Jiang, L.; Lu, W. Organometallics 2006, 25, 5973.
  (b) Kar, A.; Mangu, N.; Kaiser, H. M.; Tse, M. K. J. Organomet. Chem. 2009, 694, 524.
  (c) Zhou, L.; Lu, W. Organometallics 2012, 31, 2124.
5. [5]
  (a) Ye, M. C.; Edmunds, A.; Morris, J.; Sale, D.; Zhang, Y.; Yu, J. Q. Chem. Sci. 2013, 4, 2374.
  (b) Han, J.; Liu, P.; Wang, C.; Wang, Q.; Zhang, J. Y.; Zhao, Y. W.; Shi, D. Q.; Huang, Z. B.; Zhao, Y. S. Org. Lett. 2014, 16, 5682.
  (c) Yang, Z.; Qiu, F. C.; Gao, J.; Li, Z. W.; Guan, B. T. Org. Lett. 2015, 17, 4316.
  (d) Xu, J. C.; Liu, Y.; Wang, Y.; Li, Y. J.; Xu, X. H.; Jin, Z. Org. Lett. 2017, 19, 1562.
  (e) Hu, Y. H.; Xu, Z.; Shao, L. Y.; Ji, Y. F. Synlett 2018, 29, 1875.
  (f) Yang, J. Y.; Fu, X. P.; Tang, S. B.; Deng, K. Z.; Zhang, L. L.; Yang, X. J.; Ji, Y. F. J. Org. Chem. 2019, 84, 10221.
6. [6]
  (a) Deprez, N.; Sanford, M. S. J. Am. Chem. Soc. 2009, 131, 11234.
  (b) Li, W.; Yin, Z.; Jiang, X.; Sun, P. J. Org. Chem. 2011, 76, 8543.
  (c) Guo, D. D.; Li, B.; Guo, S. H.; Pan, G. F.; Gao, Y. R.; Wang, Y. Q. ChemCatChem 2017, 9, 2001.
7. [7]
  (a) Shabasho, D.; Daugulis, O. J. Am. Chem. Soc. 2010, 132, 3965.
  (b) Yokota, A.; Aihara, Y.; Chatani, N. J. Org. Chem. 2014, 79, 11922.
8. [8]
  (a) Sun, C. L.; Liu, N.; Li, B. J.; Yu, D. G.; Wang, Y.; Shi, Z. J. Org. Lett. 2010, 12, 184.
  (b) Thirunavukkarasu, V. S.; Cheng, C. H. Chem.-Eur. J. 2011, 17, 14723.
  (c) Shao, L. Y.; Xing, L. H.; Guo, Y.; Yu, K. K.; Wang, W.; Liu, H. W.; Liao, D. H.; Ji, Y. F. Adv. Synth. Catal. 2018, 360, 2925.
9. [9]
  Li, W.; Xu, Z.; Sun, P.; Jiang, X.; Fan, M. Org. Lett. 2011, 13, 1286. doi: 10.1021/ol103075n
10. [10]
  (a) Nishikata, T.; Abela, A. R.; Lipshutz, B. H. Angew. Chem., Int. Ed. 2010, 49, 781.
  (b) Jiang, Z.; Zhang, L.; Dong, C.; Su, X.; Li, H.; Tang, W.; Xu, L.; Fan, Q. RSC Adv. 2013, 3, 1025.
  (c) Li, D.; Xu, N.; Zhang, Y.; Wang, L. Chem. Commun. 2014, 50, 14862.
11. [11]
  Zhang, Q.; Yin, X. S.; Zhao, S.; Fang, S. L.; Shi, B. F. Chem. Commun. 2014, 50, 8353.
12. [12]
  (a) Cernak, T.; Dykstra, K. D.; Tyagarajan, S.; Vachal, P.; Krska, S. W. Chem. Soc. Rev. 2016, 45, 546.
  (b) Margrey, K. A.; Czaplyski, W. L.; Nicewicz, D. A.; Alexanian, E. J. J. Am. Chem. Soc. 2018, 140, 4213.
  (c) Brodney, M. A.; Sharma, R.; Lazzaro, J. T.; Walker, G. S.; Obach, R. S. Bioorg. Med. Chem. Lett. 2018, 28, 2068.
  (d) Graßl, S.; Chen, Y. H.; Hamze, C.; Tüllmann, C. P.; Knochel, P. Org. Lett. 2019, 21, 494.
13. [13]
  (a) Paulis, T. D.; Hemstapat, K.; Chen, Y. L.; Zhang, Y. Q.; Saleh, S.; Alagille, D.; Baldwin, R. M.; Tamagnan, G. D.; Conn, P. J. J. Med. Chem. 2006, 49, 3332.
  (b) Lahm, G. P.; Cordova, D.; Barry, J. D. Bioorg. Med. Chem. 2009, 17, 4127.
  (c) Mowbray, C. E.; Burt, C.; Corbau, R.; Gayton, S.; Hawes, M.; Perros, M.; Tran, I.; Price, D. A.; Quinton, F. J.; Selby, M. D.; Stupple, P. A.; Webster, R.; Wood, A. Bioorg. Med. Chem. Lett. 2009, 19, 5857.
  (d) Alvarez, G.; Varela, J.; Cruces, E.; Fernández, M.; Gabay, M.; Leal, S. M.; Escobar, P.; Sanabria, L.; Serna, E.; Torres, S.; Thiel, S. J. F.; Yaluff, G.; Vera de Bilbao, N. I.; Cerecetto, H.; González, M. Antimicrob. Agents Chemother. 2015, 59, 1398.
14. [14]
  (a) Shabashov, D.; Daugulis, O. Org. Lett. 2005, 7, 3657.
  (b) Cheng, K.; Zhang, Y.; Zhao, J.; Xie, C. Synlett 2008, 1325.
  (c) Umeda, N.; Hirano, K.; Satoh, T.; Miura, M. J. Org. Chem. 2009, 74, 7094.
  (d) Arockiam, P. B.; Fischmeister, C.; Bruneau, C.; Dixneuf, P. H. Green Chem. 2011, 13, 3075.
  (e) Thirunavukkarasu, V. S.; Raghuvanshi, K.; Ackermann, L. Org. Lett. 2013, 15, 3286.
  (f) Yu, X.; Yu, S.; Xiao, J.; Wan, B.; Li, X. J. Org. Chem. 2013, 78, 5444.
  (g) Liu, P. M.; Frost, C. G. Org. Lett. 2013, 15, 5862.
  (h) Fabre, I.; Wolff, N.; Duc, G.; Flegeau, E.; Bruneau, C.; Dixneuf, P.; Jutand, A. Chem.-Eur. J. 2013, 19, 7595.
  (i) Lu, M. Z.; Lu, P.; Xu, Y. H.; Loh, T.-P. Org. Lett. 2014, 16, 2614.
  (j) Han, S.; Sharma, S.; Park, J.; Kim, M.; Shin, Y.; Mishra, N. K.; Bae, J. J.; Kwak, J. H.; Jung, Y. H.; Kim, I. S. J. Org. Chem. 2014, 79, 275.
  (k) Reddy, G. M.; Rao, N. S.; Satyanarayana, P.; Maheswaran, H. RSC Adv. 2015, 5, 105347.
  (l) Yang, P.; Bao, Y. S. RSC Adv. 2017, 7, 53878.
  (m) Kwak, S. H.; Gulia, N.; Daugulis, O. J. Org. Chem. 2018, 83, 5844.
  (n) Abidi, O.; Boubaker, T.; Hierso, J.; Roger, J. Org. Biomol. Chem. 2019, 17, 5916.
15. [15]
  (a) Fan, X. M.; Guo, Y.; Li, Y. D.; Yu, K. K.; Liu, H. W.; Liao, D. H.; Ji, Y. F. Asian J. Org. Chem. 2016, 5, 499.
  (b) Chen, M. M.; Shao, L. Y.; Lun, L. J.; Wu, Y. L.; Fu, X. P.; Ji, Y. F. Chin. Chem. Lett. 2019, 30, 702.
16. [16]
  Ren, Z.; Dong, G. B. Organometallics 2016, 35, 1057.
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1.
沈阳化工大学材料科学与工程学院沈阳 110142

Fully Substituted Pyrazoles Assisted Palladium-Catalyzed Late-Stage Arylation of C(sp2)—H Bond

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通讯作者: 陈斌, bchen63@163.com

Fully Substituted Pyrazoles Assisted Palladium-Catalyzed Late-Stage Arylation of C(sp²)—H Bond