Citation: Huan Li, Yuxuan Han, Zi Yang, Zhenyu Yao, Lianhui Wang, Xiuling Cui. Rh(Ⅲ)-catalyzed annulation of azobenzenes and α-Cl ketones toward 3-acyl-2H-indazoles[J]. Chinese Chemical Letters, ;2021, 32(5): 1709-1712. doi: 10.1016/j.cclet.2020.12.027 shu

Rh(Ⅲ)-catalyzed annulation of azobenzenes and α-Cl ketones toward 3-acyl-2H-indazoles

Engineering Research Centre of Molecular Medicine of Ministry of Education, Key Laboratory of Fujian Molecular Medi-cine, Key Laboratory of Precision Medicine and Molecular Diagnosis of Fujian Universities, Key Laboratory of Xiamen Marine and Gene Drugs, School of Biomedical Sciences, Huaqiao University, Xiamen 361021, China

cuixl@hqu.edu.cn

Received Date: 8 October 2020
Revised Date: 16 December 2020
Accepted Date: 17 December 2020
Available Online: 20 December 2020

Figures(5)

Rhodium(Ⅲ)-catalyzed [4 + 1] cyclization of azobenzenes with α-Cl ketones has been developed. 3-Acyl-2H-indazoles could be easily afforded in up to 97% yields for more than 30 examples. The obtained products are potentially valuable in organic synthesis and drug discovery. This protocol featured with high efficiency, extensive functional group tolerance and mild reaction conditions. The one-step efficient construction of an anti-inflammatory agent confirms the practicability of this procedure.
- Rh(Ⅲ)-catalyzed,
- C-H activation/cyclization,
- α-Cl Ketones,
- 3-Acyl-2H-indazoles
1. [1]
  (a) J.D. Rodgers, B.L. Johnson, C.W. Chang, et al., Bioorg. Med. Chem. Lett. 6 (1996) 2919-2924;
  (b) S. Bräse, C. Gil, K. Knepper, Bioorg. Med. Chem. Lett. 10 (2002) 2415-2437;
  (c) H. Cerecetto, A. Gerpe, M. Gonza'lez, V.J. Ara'n, C.O. de Oca'riz, Mini-Rev. Med. Chem. 5 (2005) 869-878;
  (d) J. Magano, M. Waldo, D. Greene, E. Nord, Org. Process Res. Dev. 12 (2008) 877-883;
  (e) M.J. Haddadin, W.E. Conrad, M.J. Kurth, Mini-Rev. Med. Chem. 12 (2012) 1293-1300.
2. [2]
  (a) L.J. Huang, M.L. Shih, H.S. Chen, et al., Bioorg. Med. Chem. 14 (2006) 528-536;
  (b) R.J. Steffan, E.M. Matelan. WO 2006/050006A2, 2006;
  (c) R. Halim, M. Harding, R. Hufton, et al., WO 2012/051659A1, 2012;
  (d) Y. Jia, J. Zhang, J. Feng, et al., Chem. Biol. Drug Des. 83 (2014) 306-316;
  (e) W. Aman, J. Lee, M. Kim, et al., Med. Chem. Lett. 26 (2016) 1188-1192
3. [3]
  (a) M.D. Angelis, F. Stossi, K.A. Carlson, B.S. Katzenellenbogen, J.A. Katzenellenbogen, J. Med. Chem. 48 (2005) 1132-1144;
  (b) G. Luo, L. Chen, G. Dubowchik, J. Org. Chem. 71 (2006) 5392-5395;
  (c) A. Bunnell, C. O'Yang, A. Petrica, M.J. Soth, Synth. Commun. 36 (2006) 285-293;
  (d) C. Wu, Y. Fang, R.C. Larock, F. Shi, Org. Lett. 12 (2010) 2234-2237;
  (e) M.R. Kumar, A. Park, N. Park, S. Lee, Org. Lett. 13 (2011) 3542-2545;
  (f) A. Unsinn, P. Knochel, Chem. Commun. 48 (2012) 2680-2682;
  (g) W.S. Yong, S. Park, H. Yun, P.H. Lee, Adv. Synth. Catal. 358 (2016) 1958-1967;
  (h) Z.A. Henley, B.D. Bax, L.M. Inglesby, et al., ACS Med. Chem. Lett. 8 (2017) 1093-1098;
  (i) J.S. Zhu, N. Kraemer, M.E. Shatskikh, et al., Org. Lett. 20 (2018) 4736-4739;
  (j) Q. Gao, X. Han, P. Tong, et al., Org. Lett. 21 (2019) 6074-6078.
4. [4]
  (a) L. Ackermann, Chem. Rev. 111 (2011) 1315-1345;
  (b) S.H. Cho, J.Y. Kim, J. Kwak, S. Chang, Chem. Soc. Rev. 40 (2011) 5068-5083;
  (c) N. Kuhl, M.N. Hopkinson, J. Wencel-Delord, F. Glorius, Angew. Chem. Int. Ed. 51 (2012) 10236-10254;
  (d) G. Rouquet, N. Chatani, Angew. Chem. Int. Ed. 52 (2013) 11726-11743;
  (e) S.D. DeSarkar, W. Liu, S.I. Kozhushkov, L. Ackermann, Adv. Synth. Catal. 356 (2014) 1461-1479;
  (f) S.A. Girard, T. Knauber, C.J. Li, Angew. Chem. Int. Ed. 53 (2014) 74-100;
  (g) O. Daugulis, J. Roane, L.D. Tran, Acc. Chem. Res. 48 (2015) 1053-1064;
  (h) Z. Huang, H.N. Lim, F. Mo, M.C. Young, G. Dong, Chem. Soc. Rev. 44 (2015) 7764-7786;
  (i) Z. Chen, B. Wang, Y. Zhang, et al., Org. Chem. Front. 2 (2015) 1107-1295;
  (j) W. Liu, L. Ackermann, ACS Catal. 6 (2016) 3743-3752;
  (k) C. Sambiagio, D. Schonbauer, M. Schnürch, et al., Chem. Soc. Rev. 47 (2018) 6603-6743;
  (l) X. Han, P.P. Lin, Q. Li, Chin. Chem. Lett. 30 (2019) 1495-1502.
5. [5]
  (a) T. Zhou, B. Li, B. Wang, Org. Lett. 22 (2016) 5066-5069;
  (b) P. Hu, Y. Zhang, B. Liu, X. Li, Org. Chem. Front. 5 (2018) 3263-3266;
  (c) L. Wang, D. Xiong, L. Jie, C. Yu, X. Cui, Chin. Chem. Lett. 29 (2018) 907-910;
  (d) Z. Shen, C. Pi, X. Cui, Y. Wu, Chin. Chem. Lett. 30 (2019) 1374-1378;
  (e) X. Song, B.N.D. Doan, X. Zhang, R. Lee, X. Fan, Org. Lett. 2 (2020) 46-51.
6. [6]
  (a) Y. Lian, R.G. Bergman, L.D. Lavis, J.A. Ellman, J. Am. Chem. Soc. 135 (2013) 7122-7125;
  (b) D. Zhao, Q. Wu, X. Huang, et al., Chem. Eur. J. 19 (2013) 6239-9244;
  (c) C. Qian, D. Lin, Y. Deng, et al., Org. Biomol. Chem. 12 (2014) 5866-5875;
  (d) J.R. Hummel, J.A. Ellman, J. Am. Chem. Soc. 137 (2015) 490-498;
  (e) S. Sharma, S.H. Han, I.S. Kim, et al., Org. Lett. 17 (2015) 2852-2855;
  (f) X. Geng, C. Wang, Org. Lett. 17 (2015) 2434-2467;
  (g) T. Jeong, S.H. Han, et al., Org. Lett. 18 (2016) 232-235;
  (h) G. Hong, A.N. Aruma, X. Zhu, S. Wu, L. Wang, Synthesis 48 (2016) 1147-1158;
  (i) Z. Long, Y. Yang, J. You, Org. Lett. 19 (2017) 2781-2784;
  (j) S. Cai, S. Lin, X. Yi, C. Xi, J. Org. Chem. 82 (2017) 512-520;
  (k) Z. Long, Z. Wang, D. Zhou, D. Wan, J. You, Org. Lett. 19 (2017) 2777-2780;
  (l) X. Chen, G. Zheng, G. Song, X. Li, Adv. Synth. Catal. 360 (2018) 2836-2842;
  (m) R. Chun, S. Kim, I.S. Kim, et al., Adv. Synth. Catal. 361 (2019) 1-11;
  (n) J. Zhu, S. Sun, J. Cheng, Tetrahedron Lett. 59 (2018) 2284-2287;
  (o) H. Oh, S. Han, A.K. Pandey, et al., J. Org. Chem. 83 (2018) 4070-4077.
7. [7]
  D.G. Yu, F. de Azambuja, F. Glorius, Angew. Chem. Int. Ed. 53(2014) 2754-2758. doi: 10.1002/anie.201310272
8. [8]
  J. Li, Z. Zhang, M. Tang, X. Zhang, J. Jin, Org. Lett. 18(2016) 3898-3901. doi: 10.1021/acs.orglett.6b01916
9. [9]
  (a) C. Yang, F. Song, J. Chen, Y. Huang, Adv. Synth. Catal. 359 (2017) 3496-3502;
  (b) C. Xie, Z. Dai, Y. Niu, C. Ma, J. Org. Chem. 83 (2018) 2317-2323;
  (c) R.A. Bohmann, J.H. Schoebel, Y. Unoh, M. Miura, C. Bolm, Adv. Synth. Catal. 361 (2019) 2000-2003;
  (d) H. Liu, C. Wu, H. Liu, J. Wang, J. Org. Chem. 84 (2019) 13262-13275.
10. [10]
  J. Zhou, J. Li, H. Liu, et al., Org. Lett. 20(2018) 7645-7649. doi: 10.1021/acs.orglett.8b03383
11. [11]
  (a) S. Patai, Z. Rappoport, The Chemistry of α-Haloketones, α-Haloaldehydes and α-Haloimines, Wiley, New York, 1988, pp. 1-489;
  (b) W.A. Erian, M.S. Sherif, M.H. Gaber, Molecules 8 (2003) 793-865.
12. [12]
  (a) L. Xu, L. Wang, X. Cui, et al., Org. Lett. 19 (2017) 4343-4346;
  (b) Y. Feng, N. Tian, Y. Li, et al., Org. Lett. 19 (2017) 1658-1661;
  (c) Y. Yu, Y. Feng, R. Chauvin, et al., Org. Lett. 20 (2018) 4209-4212;
  (d) Z. Yang, Z. Song, L. Wang, L. Jie, X. Cui, Chem. Commun. 55 (2019) 6094-6097;
  (e) B. Wu, Z. Yang, H. Zhang, L. Wang, X. Cui, Chem. Commun. 55 (2019) 4190-4193;
  (f) S. Du, C. Pi, T. Wan, Y. Wu, X. Cui, Adv. Synth. Catal. 361 (2019) 1766-1770;
  (g) S. Huang, H. Li, X. Sun, et al., Org. Lett. 21 (2019) 5570-5774;
  (h) J. Ren, X. Yan, X. Cui, et al., Green Chem. 22 (2020) 265-269;
  (i) Y. Wu, C. Pi, X. Cui, Y. Wu, Org. Lett. 22 (2020) 361-364;
  (j) Y. He, C. Pi, Y. Wu, X. Cui, Chin. Chem. Lett. 31 (2020) 396-400.
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]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  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
6. [6]
  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
7. [7]
  Peiyan Zhu , Yanyan Yang , Hui Li , Jinhua Wang , Shiqing Li . Rh(Ⅲ)‐Catalyzed sequential ring‐retentive/‐opening [4 + 2] annulations of 2H‐imidazoles towards full‐color emissive imidazo[5,1‐a]isoquinolinium salts and AIE‐active non‐symmetric 1,1′‐biisoquinolines. Chinese Chemical Letters, 2024, 35(10): 109533-. doi: 10.1016/j.cclet.2024.109533
8. [8]
  Weimei Zeng , Youai Qiu . Electrochemical C-H carboxylation of benzylamines. Chinese Chemical Letters, 2026, 37(1): 111679-. doi: 10.1016/j.cclet.2025.111679
9. [9]
  Chao Chen , Wenwen Yu , Guangen Huang , Xuelian Ren , Xiangli Chen , Yixin Li , Shenggui Liang , Mengmeng Xu , Mingyue Zheng , Yaxi Yang , He Huang , Wei Tang , Bing Zhou . Asymmetric macrocyclization enabled by Rh(Ⅲ)-catalyzed CH activation: Enantioenriched macrocyclic inhibitor of Zika virus infection. Chinese Chemical Letters, 2024, 35(11): 109574-. doi: 10.1016/j.cclet.2024.109574
10. [10]
  Qiao Song , Xue Peng , Zhouyu Wang , Leyong Wang . Iron-catalyzed C–H activation: A sustainable approach to efficient organic synthesis. Chinese Chemical Letters, 2025, 36(5): 110869-. doi: 10.1016/j.cclet.2025.110869
11. [11]
  Xinghui Yao , Zhouyu Wang , Da-Gang Yu . Sustainable electrosynthesis: Enantioselective electrochemical Rh(III)/chiral carboxylic acid-catalyzed oxidative CH cyclization coupled with hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(9): 109916-. doi: 10.1016/j.cclet.2024.109916
12. [12]
  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
13. [13]
  Lihui Ou , Zhancheng Liu , Dai-Huo Liu , Zhi Zhang . Cl-adsorbed Cu(111)/H₂O interface selectively realizes electrochemical CO₂ reduction towards C₂H₄ product: Mechanistic understanding. Chinese Chemical Letters, 2026, 37(2): 111920-. doi: 10.1016/j.cclet.2025.111920
14. [14]
  Fangxiang SUN , Qing ZHANG , Yifan ZHANG , Haoyi SUN , Akim V. Shmal′ko , Sergey A. Anufriev , Igor B. Sivaev , Deshuang TU , Hong YAN . Pd-catalyzed B—H bond activation and annulation of nido-carborane with terminal olefins: Facile construction of 2D-3D fused polycyclic compounds. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 467-478. doi: 10.11862/CJIC.20250347
15. [15]
  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
16. [16]
  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
17. [17]
  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
18. [18]
  Xinghao Cai , Chen Ma , Ying Kang , Yuqiang Ren , Xue Meng , Wei Lu , Shiming Fan , Shouxin Liu . Nickel-catalyzed C(sp²)–H alkynylation of free α-substituted benzylamines using a transient directing group. Chinese Chemical Letters, 2025, 36(10): 110901-. doi: 10.1016/j.cclet.2025.110901
19. [19]
  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
20. [20]
  Huahong ZHANG , Yang ZHAO , Rui NING , Shuixing WU , Xiaopeng ZHANG . Coordination equilibrium between cyclometalated Pt(Ⅱ) complexs [Pt(κ³-N^C^N′)(CNXyl)]Cl and [Pt(κ²-N^C^N′)(CNXyl)Cl]. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1840-1850. doi: 10.11862/CJIC.20250136

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(2490)
HTML views(228)

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