Citation: Li Yao, Ma Lifang, Wang Xiaojiao, Lei Bowen, Zhao Yi, Yang Jiayu, Li Ziyuan. Palladium(Ⅱ)-Catalyzed Homocoupling of Oxazole/Thiazole in Absence of Silver Oxidant[J]. Chinese Journal of Organic Chemistry, ;2017, 37(5): 1213-1219. doi: 10.6023/cjoc201612052 shu

Palladium(Ⅱ)-Catalyzed Homocoupling of Oxazole/Thiazole in Absence of Silver Oxidant

Department of Pharmaceutical and Biological Engineering, School of Chemical Engineering, Sichuan University, Chengdu 610065

Corresponding author: Ma Lifang, mlfang11@scu.edu.cn Li Ziyuan, liziyuan@scu.edu.cn
Received Date: 20 December 2016
Revised Date: 9 March 2017

Fund Project: by the Fundamental Research Funds for the Central Universities 2016SCU11020

Figures(3)

Homocoupling of oxazole/thiazole via palladium-catalyzed C-H bond activation using oxone as an oxidant has been achieved in moderate to excellent yields with good functional group tolerance. No other additive or ligand was employed in this efficient reaction. Comparing to our previously reported homocoupling of oxazole/thiazole, the absence of stoichiometric silver oxidant renders this reaction more environment-benign and cost-effective. A preliminary mechanism involving a Pd^Ⅱ/Pd^Ⅳ catalytic cycle is also proposed. Further exploration of this environmental-benign oxidant on other categories of coupling reactions, as well as applications of this revised homocoupling to structural modification of oxazole/thiazole-containing natural products, are undergoing in our lab.
- thiazole,
- oxazole,
- homocoupling,
- C-H bond activation,
- oxone
1. [1]
  (a) Taori, K. ; Paul, V. J. ; Luesch, H. J. Am. Chem. Soc. 2008, 130, 1806. (b) Wright, A. E. ; Botelho, J. C. ; Guzman, E. ; Harmody, D. ; Linley, P. ; McCarthy, P. J. ; Pitts, T. P. ; Pomponi, S. A. ; Reed, J. K. J. Nat. Prod. 2007, 70, 412. (c) Hofle, G. ; Bedorf, N. ; Steinmetz, H. ; Schomburg, D. ; Gerth, K. ; Reichenbach, H. Angew. Chem. , Int. Ed. 1996, 35, 1567. (d) Oku, N. ; Takada, K. ; Fuller, R. W. ; Wilson, J. A. ; Peach, M. L. ; Pannell, L. K. ; McMahon, J. B. ; Gustafson, K. R. J. Am. Chem. Soc. 2010, 132, 10278.
2. [2]
  (a) Li, Y. -M. ; Milne, J. C. ; Madison, L. L. ; Kolter, R. ; Walsh, C. T. Science 1996, 274, 1188. (b) Walsh, C. T. Science 2004, 303, 1805.
3. [3]
  (a) Liu, C. ; Yuan, J. ; Gao, M. ; Tang, S. ; Li, W. ; Shi, R. ; Lei, A. Chem. Rev. 2015, 115, 12138. (b) Yang, L. ; Huang, H. Chem. Rev. 2015, 115, 3468. (c) Cheng, C. ; Hartwig, J. F. Chem. Rev. 2015, 115, 8946. (d) Ackermann, L. Chem. Rev. 2011, 111, 1315. (e) Sun, C. -L. ; Li, B. -J. ; Shi, Z. -J. Chem. Rev. 2011, 111, 1293. (f) Lyons, T. W. ; Sanford, M. S. Chem. Rev. 2010, 110, 1147. (g) Denise, A. C. ; Bergman, R. G. ; Ellman, J. A. Chem. Rev. 2010, 110, 624. (h) Chen, X. ; Engle, K. M. ; Wang, D. -H. ; Yu, J. -Q. Angew. Chem. , Int. Ed. 2009, 48, 5094. (i) Wang, L. ; Li, Z. ; Wan, K. ; Qu, X. ; Hu, S. ; Wang, F. Chin. J. Org. Chem. 2016, 36, 889 (in Chinese). (王亮, 李站, 万康, 瞿星, 胡思前, 王锋, 有机化学, 2016, 36, 889. ) (j) He, J. ; Lou, S. ; Xu, D. Chin. J. Org. Chem. 2016, 36, 1218 (in Chinese). (何将旗, 娄绍杰, 许丹倩, 有机化学, 2016, 36, 1218. ) (k) Lu, B. ; Li, X. ; Lin, Y. Chin. J. Org. Chem. 2015, 35, 2275 (in Chinese). (卢贝丽, 李现艳, 林咏梅, 有机化学, 2015, 35, 2275. ) (l) Tan, M. ; Gu, Y. ; Luo, X. ; Zhang, P. Chin. J. Org. Chem. 2015, 35, 781 (in Chinese). (谭明雄, 顾运琼, 罗旭健, 张培, 有机化学, 2015, 35, 781. ) (m) Gang, F. ; Xu, G. ; Dong, T. ; Yang, L. ; Du, Z. Chin. J. Org. Chem. 2015, 35, 1428 (in Chinese). (刚芳莉, 徐光利, 董涛生, 杨丽, 杜正银, 有机化学, 2015, 35, 1428. ) (n) Tang, M. ; Huo, X. ; Meng, Q. ; Zhang, W. Acta Chim. Sinica 2016, 74, 219 (in Chinese). (汤淏溟, 霍小红, 孟庆华, 张万斌, 化学学报, 2016, 74, 219. ) (o) Yu, J. ; Ding, K. Acta Chim. Sinica 2015, 73, 1223 (in Chinese). (余金权, 丁奎岭, 化学学报, 2015, 73, 1223. ) (p) Zhou, L. ; Lu, W. Acta Chim. Sinica 2015, 73, 1250 (in Chinese). (周励宏, 陆文军, 化学学报, 2015, 73, 1250. ) (q) Shang, X. ; Liu, Z. Acta Chim. Sinica 2015, 73, 1275 (in Chinese). (尚筱洁, 柳忠全, 化学学报, 2015, 73, 1275. ) (r) Liao, G. ; Shi, B. Acta Chim. Sinica 2015, 73, 1283 (in Chinese). (廖港, 史炳锋, 化学学报, 2015, 73, 1283. )
4. [4]
  (a) Harari, M. ; Couly, F. ; Fruit, C. ; Besson, T. Org. Lett. 2016, 18, 3282. (b) Gu, J. ; Cai, C. RSC Adv. 2015, 5, 56311. (c) Bon, J. L. ; Feng, D. ; Marder, S. R. ; Blakey, S. B. J. Org. Chem. 2014, 79, 7766. (d) Ferguson, D. M. ; Rudolph, S. R. ; Kalyani, D. ACS Catal. 2014, 4, 2395. (e) Chen, X. ; Huang, X. ; He, Q. ; Xie, Y. ; Yang, C. Chem. Commun. 2014, 50, 3996. (f) Liu, W. ; Yu, X. ; Kuang, C. Org. Lett. 2014, 16, 1798. (g) Fu, X. -P. ; Xuan, Q. -Q. ; Liu, L. ; Wang, D. ; Chen, Y. -J. ; Li, C. -J. Tetrahedron 2013, 69, 4436. (h) Dong, J. ; Huang, Y. ; Qin, X. ; Cheng, Y. ; Hao, J. ; Wan, D. ; Li, W. ; Liu, X. ; You, J. Chem. Eur. J. 2012, 18, 6158. (i) Wu, G. ; Zhou, J. ; Zhang, M. ; Hu, P. ; Su, W. Chem. Commun. 2012, 48, 8964.
5. [5]
  (a) Lohrey, L. ; Uehara, T. N. ; Tani, S. ; Yamaguchi, J. ; Humpf, H. -U. ; Itami, K. Eur. J. Org. Chem. 2014, 3387. (b) Sekizawa, H. ; Amaike, K. ; Itoh, Y. ; Suzuki, T. ; Itami, K. ; Yamaguchi, J. ACS Med. Chem. Lett. 2014, 5, 582. (c) Tani, S. ; Uehara, T. N. ; Yamaguchi, J. ; Itami, K. Chem. Sci. 2014, 5, 123. (d) Shibahara, F. ; Yamauchi, T. ; Yamaguchi, E. ; Murai, T. J. Org. Chem. 2012, 77, 8815. (e) Kirchberg, S. ; Tani, S. ; Ueda, K. ; Yamaguchi, J. ; Studer, A. ; Itami, K. Angew. Chem. , Int. Ed. 2011, 50, 2387.
6. [6]
  (a) Heiskanen, J. P. ; Vivo, P. ; Saari, N. M. ; Hukka, T. I. ; Kastinen, T. ; Kaunisto, K. ; Lemmetyinen, H. J. ; Hormi, O. E. O. J. Org. Chem. 2016, 81, 1535. (b) Gao, S. ; Yang, C. ; Huang, Y. ; Zhao, L. ; Wu, X. ; Yao, H. ; Lin, A. Org. Biomol. Chem. 2016, 14, 840. (c) Liu, X. -W. ; Shi, J. -L. ; Wei, J. -B. ; Yang, C. ; Yan, J. -X. ; Peng, K. ; Dai, L. ; Li, C. -G. ; Wang, B. -Q. ; Shi, Z. -J. Chem. Commun. 2015, 51, 4599. (d) Zhou, H. ; Gai, K. ; Lin, A. ; Xu, J. ; Wu, X. ; Yao, H. Org. Biomol. Chem. 2015, 13, 1243. (e) Chen, X. ; Huang, X. ; He, Q. ; Xie, Y. ; Yang, C. Chem. Commun. 2014, 50, 3996. (f) Liu, B. ; Huang, Y. ; Lan, J. ; Song, F. ; You, J. Chem. Sci. 2013, 4, 2163. (g) Chen, L. ; Bruneau, C. ; Dixneuf, P. H. ; Doucet, H. ChemCatChem 2013, 5, 1956. (h) Yan, T. ; Chen, L. ; Bruneau, C. ; Dixneuf, P. H. ; Doucet, H. J. Org. Chem. 2013, 78, 4177.
7. [7]
  (a) Li, Z. ; Ma, L. ; Xu, J. ; Kong, L. ; Wu, X. ; Yao, H. Chem. Commun. 2012, 48, 3763. (b) Li, Z. ; Zhou, H. ; Xu, J. ; Wu, X. , Yao, H. Tetrahedron 2013, 69, 3281. (c) Li, Z. ; Ma, L. ; Tang, C. ; Xu, J. ; Wu, X. ; Yao, H. Tetrahedron Lett. 2011, 52, 5643. (d) Li, Z. ; Wang, Y. ; Huang, Y. ; Tang, C. ; Xu, J. ; Wu, X. ; Yao, H. Tetrahedron 2011, 67, 5550.
8. [8]
  (a) Liang, Y. -F. ; Wang, X. ; Yuan, Y. ; Liang, Y. ; Li, X. ; Jiao, N. ACS Catal. 2015, 5, 6148. (b) Desai, L. V. ; Malik, H. A. ; Sanford, M. S. Org. Lett. 2006, 8, 1141. (c) Hussain, H. ; Green, I. R. ; Ahmed, I. Chem. Rev. 2013, 113, 3329.
9. [9]
  (a) Perez, L. J. ; Faulkner, D. J. J. Nat. Prod. 2003, 66, 247. (b) Foster, M. P. ; Concepcion, G. P. ; Garaan, G. B. ; Ireland, C. M. J. Org. Chem. 1992, 57, 6671.
10. [10]
  (a) Huang, Y. ; Gan, H. ; Li, S. ; Xu, J. ; Wu, X. ; Yao, H. Tetrahedron Lett. 2010, 51, 1751. (b) Huang, Y. ; Ni, L. ; Gan, H. ; He, Y. ; Xu, J. ; Wu, X. ; Yao, H. Tetrahedron 2011, 67, 2066. (c) Wang, Y. ; Li, Z. ; Huang, Y. ; Tang, C. ; Wu, X. ; Xu, J. ; Yao, H. Tetrahedron 2011, 67, 7406.
1. [1]
  Chengyu JIANG , Xufeng LIU . Synthesis, structural characterization, electrocatalytic proton reduction, and fungicidal activity of thiazole-containing di-iron complexes. Chinese Journal of Inorganic Chemistry, 2026, 42(2): 355-364. doi: 10.11862/CJIC.20250253
2. [2]
  Qiuyun Li , Yannan Zhu , Yining Wang , Gang Qi , Wen-Juan Hao , Kelu Yan , Bo Jiang . Catalytic CH activation-initiated transdiannulation: An oxygen transfer route to ring-fluorinated tricyclic γ-lactones. Chinese Chemical Letters, 2024, 35(9): 109494-. doi: 10.1016/j.cclet.2024.109494
3. [3]
  Yanjie Lv , Xinyu Zhao , Jing Sun , Huiying Sun , Wenxi Zhang , Yuhan Cui , Xiao Li , Zhongmin Su . Atomic-level regulation of POMOF homologous isomer for photocatalytic C-H bond oxidation. Chinese Chemical Letters, 2026, 37(10): 113018-. doi: 10.1016/j.cclet.2026.113018
4. [4]
  Xiao Tang , Erik V. Van der Eycken , Liangliang Song . Transition metal-catalyzed C-H activation/annulation for the construction of unnatural amino acids and peptides. Chinese Chemical Letters, 2026, 37(2): 111678-. doi: 10.1016/j.cclet.2025.111678
5. [5]
  Weimei Zeng , Youai Qiu . Electrochemical C-H carboxylation of benzylamines. Chinese Chemical Letters, 2026, 37(1): 111679-. doi: 10.1016/j.cclet.2025.111679
6. [6]
  Xiangyang Ji , Yishuang Chen , Peng Zhang , Shaojia Song , Jian Liu , Weiyu Song . Boosting the first C–H bond activation of propane on rod-like V/CeO₂ catalyst by photo-assisted thermal catalysis. Chinese Chemical Letters, 2025, 36(5): 110719-. doi: 10.1016/j.cclet.2024.110719
7. [7]
  Junhua Li , Yu Fu , Yian Shi . A rapid access to fused polycyclic indolo[2,1-a]isoquinolins via Pd-catalyzed sequential Heck/C-H activation/amination reaction with diaziridinone. Chinese Chemical Letters, 2026, 37(3): 111376-. doi: 10.1016/j.cclet.2025.111376
8. [8]
  Min Hou , Yuexin Wang , Siyu Zhang , Keke Zhang , Xiu Tan , Xianjun Lang . Thiazole-linked pyrene covalent organic framework for selective sulfoxidation via an electron transfer mediator by photoredox catalysis. Chinese Chemical Letters, 2026, 37(8): 112817-. doi: 10.1016/j.cclet.2026.112817
9. [9]
  Yumei Wu , Zhengjun Chen , Yuan Shen , Deying Tang , Huaiyu Mo , Zihan Chen , Hongyu Li , Zhe Zheng , Chunju Li , Jie Gao , Zeli Yuan . Water-soluble thiazolo[5,4-d]thiazole-based AIEgens for universal and Level 3 resolved latent fingerprint visualization. Chinese Chemical Letters, 2026, 37(9): 111889-. doi: 10.1016/j.cclet.2025.111889
10. [10]
  Wei-Bin Li , Xiao-Chao Huang , Pei Liu , Jie Kong , Guo-Ping Yang . Recent advances in directing group assisted transition metal catalyzed para-selective C-H functionalization. Chinese Chemical Letters, 2025, 36(6): 110543-. doi: 10.1016/j.cclet.2024.110543
11. [11]
  Shihaozhi Wang , Jia-Hui Shi , Shan Xu , Xue-Jing Zhang , Ming Yan . Palladium-catalyzed carbene C-H insertion reaction of non-activated arenes. Chinese Chemical Letters, 2026, 37(4): 111225-. doi: 10.1016/j.cclet.2025.111225
12. [12]
  Xin-Juan Wang , Yao-Hang Cheng , Xin-Yan Lv , Li-Ye Liang , Guang-Hui An , Guang-Ming Li . Ruthenium-catalyzed alkylarylation of alkenes via para-selective C-H functionalization of unprotected anilines. Chinese Chemical Letters, 2026, 37(8): 112154-. doi: 10.1016/j.cclet.2025.112154
13. [13]
  Mengyao Yuan , Wansen Xie , Xiaoyu Yang . Enantioselective synthesis of inherently chiral calix[4]arenes via asymmetric C-H bromination of phenols. Chinese Chemical Letters, 2026, 37(9): 112157-. doi: 10.1016/j.cclet.2025.112157
14. [14]
  Tian-Zhang Wang , Le-Yu Tang , Yu-Qiu Guan , Lingfei Hu , Gang Lu , Yu-Feng Liang . Nickel-catalyzed reductive alkynylation of ketoimines via unstrained C–C bond activation. Chinese Chemical Letters, 2025, 36(11): 111050-. doi: 10.1016/j.cclet.2025.111050
15. [15]
  Yunkang Tong , Haiqiao Huang , Haolan Li , Mingle Li , Wen Sun , Jianjun Du , Jiangli Fan , Lei Wang , Bin Liu , Xiaoqiang Chen , Xiaojun Peng . Cooperative bond scission by HRP/H₂O₂ for targeted prodrug activation. Chinese Chemical Letters, 2024, 35(12): 109663-. doi: 10.1016/j.cclet.2024.109663
16. [16]
  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
17. [17]
  Yujing HUANG , Yuan GOU , Kexin JI , Xingcai HUANG , Siyuan CHEN , Jiaojiao KONG , Yanqing WANG . Thiazolo[5,4-d]thiazole fluorophore functionalization in 2D Cd(Ⅱ) metal-organic frameworks triggering a luminescence enhancement for highly sensitive aqueous antibiotic sensing. Chinese Journal of Inorganic Chemistry, 2026, 42(9): 1945-1958. doi: 10.11862/CJIC.20260147
18. [18]
  Xin Li , Jia-Min Lu , Bo Li , Chen Zhao , Bei-Bei Yang , Li Li . Chiroptical sensing for remote chiral amines via a C–H activation reaction. Chinese Chemical Letters, 2025, 36(5): 110310-. doi: 10.1016/j.cclet.2024.110310
19. [19]
  Yongli Zhao , Dingsheng Cao , Jie-Ping Wan , Yunyun Liu . Synthesis of 3-phosphinyl chromones via in situ iodination mediated C-H phosphination and the tunable synthesis of 2-phosphoryl chromanones. Chinese Chemical Letters, 2026, 37(1): 111740-. doi: 10.1016/j.cclet.2025.111740
20. [20]
  Guoju Guo , Xufeng Li , Jie Ma , Yongjia Shi , Jian Lv , Daoshan Yang . Photocatalyst/metal-free sequential C–N/C–S bond formation: Synthesis of S-arylisothioureas via photoinduced EDA complex activation. Chinese Chemical Letters, 2024, 35(11): 110024-. doi: 10.1016/j.cclet.2024.110024

Get Citation

PDF

XML

Metrics

PDF Downloads(22)
Abstract views(2308)
HTML views(279)

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