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.
1. [1]
  Shulei Hu , Yu Zhang , Xiong Xie , Luhan Li , Kaixian Chen , Hong Liu , Jiang Wang . Rh(Ⅲ)-catalyzed late-stage C-H alkenylation and macrolactamization for the synthesis of cyclic peptides with unique Trp(C7)-alkene crosslinks. Chinese Chemical Letters, 2024, 35(8): 109408-. doi: 10.1016/j.cclet.2023.109408
2. [2]
  Yi Luo , Lin Dong . Multicomponent remote C(sp²)-H bond addition by Ru catalysis: An efficient access to the alkylarylation of 2H-imidazoles. Chinese Chemical Letters, 2024, 35(10): 109648-. doi: 10.1016/j.cclet.2024.109648
3. [3]
  Tong Li , Leping Pan , Yan Zhang , Jihu Su , Kai Li , Kuiliang Li , Hu Chen , Qi Sun , Zhiyong Wang . Electrochemical construction of 2,5-diaryloxazoles via N–H and C(sp³)-H functionalization. Chinese Chemical Letters, 2024, 35(4): 108897-. doi: 10.1016/j.cclet.2023.108897
4. [4]
  Haoran Shi , Jiaxin Wang , Yuqin Zhu , Hongyang Li , Guodong Ju , Lanlan Zhang , Chao Wang . Highly selective α-C(sp³)-H arylation of alkenyl amides via nickel chain-walking catalysis. Chinese Chemical Letters, 2024, 35(7): 109333-. doi: 10.1016/j.cclet.2023.109333
5. [5]
  Lei Wan , Yizhou Tong , Xi Lu , Yao Fu . Cobalt-catalyzed reductive alkynylation to construct C(sp)-C(sp³) and C(sp)-C(sp²) bonds. Chinese Chemical Letters, 2024, 35(7): 109283-. doi: 10.1016/j.cclet.2023.109283
6. [6]
  Chao LIU , Jiang WU , Zhaolei JIN . Synthesis, crystal structures, and antibacterial activities of two zinc(Ⅱ) complexes bearing 5-phenyl-1H-pyrazole group. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1986-1994. doi: 10.11862/CJIC.20240153
7. [7]
  Weixu Li , Yuexin Wang , Lin Li , Xinyi Huang , Mengdi Liu , Bo Gui , Xianjun Lang , Cheng Wang . Promoting energy transfer pathway in porphyrin-based sp2 carbon-conjugated covalent organic frameworks for selective photocatalytic oxidation of sulfide. Chinese Journal of Structural Chemistry, 2024, 43(7): 100299-100299. doi: 10.1016/j.cjsc.2024.100299
8. [8]
  Yujia Shi , Yan Qiao , Pengfei Xie , Miaomiao Tian , Xingwei Li , Junbiao Chang , Bingxian Liu . Rhodium-catalyzed enantioselective in situ C(sp³)−H heteroarylation by a desymmetrization approach. Chinese Chemical Letters, 2024, 35(10): 109544-. doi: 10.1016/j.cclet.2024.109544
9. [9]
  Yuemin Chen , Yunqi Wu , Guoao Wang , Feihu Cui , Haitao Tang , Yingming Pan . Electricity-driven enantioselective cross-dehydrogenative coupling of two C(sp³)-H bonds enabled by organocatalysis. Chinese Chemical Letters, 2024, 35(9): 109445-. doi: 10.1016/j.cclet.2023.109445
10. [10]
  Shiqi Xu , Zi Ye , Shuang Shang , Fengge Wang , Huan Zhang , Lianguo Chen , Hao Lin , Chen Chen , Fang Hua , Chong-Jing Zhang . Pairs of thiol-substituted 1,2,4-triazole-based isomeric covalent inhibitors with tunable reactivity and selectivity. Chinese Chemical Letters, 2024, 35(7): 109034-. doi: 10.1016/j.cclet.2023.109034
11. [11]
  Jaeyong Ahn , Zhenping Li , Zhiwei Wang , Ke Gao , Huagui Zhuo , Wanuk Choi , Gang Chang , Xiaobo Shang , Joon Hak Oh . Surface doping effect on the optoelectronic performance of 2D organic crystals based on cyano-substituted perylene diimides. Chinese Chemical Letters, 2024, 35(9): 109777-. doi: 10.1016/j.cclet.2024.109777
12. [12]
  Shengwen Guan , Zhaotong Wei , Ningxu Han , Yude Wei , Bin Xu , Ming Wang , Junjuan Shi . Construction of metallo-complexes with 2,2′:6′,2″-terpyridine substituted triphenylamine in different modified positions and their photophysical properties. Chinese Chemical Letters, 2024, 35(7): 109348-. doi: 10.1016/j.cclet.2023.109348
13. [13]
  Ke-Ai Zhou , Lian Huang , Xing-Ping Fu , Li-Ling Zhang , Yu-Ling Wang , Qing-Yan Liu . Fluorinated metal-organic framework for methane purification from a ternary CH4/C2H6/C3H8 mixture. Chinese Journal of Structural Chemistry, 2023, 42(11): 100172-100172. doi: 10.1016/j.cjsc.2023.100172
14. [14]
  Yongheng Ren , Yang Chen , Hongwei Chen , Lu Zhang , Jiangfeng Yang , Qi Shi , Lin-Bing Sun , Jinping Li , Libo Li . Electrostatically driven kinetic Inverse CO2/C2H2 separation in LTA-type zeolites. Chinese Journal of Structural Chemistry, 2024, 43(10): 100394-100394. doi: 10.1016/j.cjsc.2024.100394
15. [15]
  Shicheng Dong , Jun Zhu . Could π-aromaticity cross an unsaturated system to a fully saturated one?. Chinese Chemical Letters, 2024, 35(6): 109214-. doi: 10.1016/j.cclet.2023.109214
16. [16]
  Dong-Xue Jiao , Hui-Li Zhang , Chao He , Si-Yu Chen , Ke Wang , Xiao-Han Zhang , Li Wei , Qi Wei . Layered (C5H6ON)2[Sb2O(C2O4)3] with a large birefringence derived from the uniform arrangement of π-conjugated units. Chinese Journal of Structural Chemistry, 2024, 43(6): 100304-100304. doi: 10.1016/j.cjsc.2024.100304
17. [17]
  Ruowen Liang , Chao Zhang , Guiyang Yan . Enhancing CO2 cycloaddition through ligand functionalization: A case study of UiO-66 metal-organic frameworks. Chinese Journal of Structural Chemistry, 2024, 43(2): 100211-100211. doi: 10.1016/j.cjsc.2023.100211
18. [18]
  Qiongqiong Wan , Yanan Xiao , Guifang Feng , Xin Dong , Wenjing Nie , Ming Gao , Qingtao Meng , Suming Chen . Visible-light-activated aziridination reaction enables simultaneous resolving of C=C bond location and the sn-position isomers in lipids. Chinese Chemical Letters, 2024, 35(4): 108775-. doi: 10.1016/j.cclet.2023.108775
19. [19]
  Tong Zhou , Xue Liu , Liang Zhao , Mingtao Qiao , Wanying Lei . Efficient Photocatalytic H₂O₂ Production and Cr(VI) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309020-. doi: 10.3866/PKU.WHXB202309020
20. [20]
  Wei Zhong , Dan Zheng , Yuanxin Ou , Aiyun Meng , Yaorong Su . K原子掺杂高度面间结晶的g-C₃N₄光催化剂及其高效H₂O₂光合成. Acta Physico-Chimica Sinica, 2024, 40(11): 2406005-. doi: 10.3866/PKU.WHXB202406005

Get Citation

PDF

XML

Metrics

PDF Downloads(22)
Abstract views(2647)
HTML views(285)

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

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

Metrics

通讯作者: 陈斌, bchen63@163.com

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