Citation: Yuping Xiong, Feihua Du, Linghui Zeng, Zhiyuan Chen. I₂/PhI(OAc)₂-assisted oxidative CH amination protocols toward metal-free pragmatic synthesis of pyrrolo[2, 3-b]indoles[J]. Chinese Chemical Letters, ;2023, 34(1): 107569. doi: 10.1016/j.cclet.2022.05.083 shu

I₂/PhI(OAc)₂-assisted oxidative CH amination protocols toward metal-free pragmatic synthesis of pyrrolo[2, 3-b]indoles

Yuping Xiong ^a ,
Feihua Du ^b ,
Linghui Zeng ^{b, *,} ,
Zhiyuan Chen ^{a, b, *,}

a.
College of Chemistry & Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China
b.
School of Medicine, Zhejiang University City College, Hangzhou 310015, China

zenglh@zucc.edu.cn

zchen@jxnu.edu.cn

Received Date: 13 December 2021
Revised Date: 23 May 2022
Accepted Date: 26 May 2022
Available Online: 29 May 2022

Figures(6)

We report herein an I₂/PhI(OAc)₂ catalytic system for the pragmatic construction of CN bonds through CH/NH oxidative coupling protocol. Divergent pyrrolo[2, 3-b]indoles were efficiently prepared via I₂-catalyzed intramolecular C–H amination reactions from (E/Z)-2-indolylenamines under metal-free conditions. Various functional groups are tolerated under mild reaction conditions and the resulting pyrrolo[2, 3-b]indoles were obtained with mostly good to excellent yields. It was interesting to observe that both the (E)- and (Z)-isomers of the starting materials were efficiently transformed into the targeted product. The I⁺-mediated catalytic cycle was proposed based on mechanistic studies for this reaction.
- CH activation,
- CH amination,
- Indole,
- Oxidative cyclization,
- aza-Heterocycle
1. [1]
  J. Lunagariya, P. Bhadja, S. Zhong, R. Vekariya, S. Xu, Mini-Rev. Med. Chem. 19 (2019) 751–761. doi: 10.2174/1389557517666170927154231
2. [2]
  A. Kumar, R. Singh, Bioorg. Chem. 89 (2019) 103021. doi: 10.1016/j.bioorg.2019.103021
3. [3]
  X. Liu, Y. Qin, Acc. Chem. Res. 52 (2019) 1877–1891. doi: 10.1021/acs.accounts.9b00246
4. [4]
  Z. Tian, P. Sun, Y. Yan, et al., Nat. Chem. Biol. 11 (2015) 259–265. doi: 10.1038/nchembio.1769
5. [5]
  W. Ding, D. Williams, P. Northcote, et al., J. Antibiot. 47 (1994) 1250–1257. doi: 10.7164/antibiotics.47.1250
6. [6]
  M. Singh, P. Petersen, N. Jacobus, et al., J. Antibiot. 47 (1994) 1258–1265. doi: 10.7164/antibiotics.47.1258
7. [7]
  T. Handa, S. Singh, I. Singh, J. Pharm. Biomed. Anal. 9 (2014) 6–17.
8. [8]
  B. Prasad, B. Sreenivas, D. Rambabu, et al., Chem. Commun. 49 (2013) 3970–3972. doi: 10.1039/c2cc38342j
9. [9]
  Q. Wu, Z. Wu, X. Qu, W. Liu, J. Am. Chem. Soc. 134 (2012) 17342–17345. doi: 10.1021/ja304829g
10. [10]
  W. Yin, X. Yu, X. Xie, S. Li, Org. Biomol. Chem. 8 (2010) 2430–2438. doi: 10.1039/c000587h
11. [11]
  S. Kenta, C. Prasanna Kumara, K. Motomu, K. Yoichiro, Chem. Eur. J. 21 (2015) 8365–8368. doi: 10.1002/chem.201501116
12. [12]
  Y. Somaraju, K. Saidulu, I. Hiriyakkanavar, J. Org. Chem. 81 (2016) 2035–2052. doi: 10.1021/acs.joc.5b02902
13. [13]
  W. Shen, Q. Sun, L. Li, et al., Nat. Commun. 8 (2017) 1748. doi: 10.1038/s41467-017-01853-1
14. [14]
  T. Liang, L. Gong, H. Zhao, H. Jiang, M. Zhang, Chem. Commun. 56 (2020) 2807–2810. doi: 10.1039/d0cc00178c
15. [15]
  Y. Du, J. Chang, J. Reiner, K. Zhao, J. Org. Chem. 73 (2008) 2007–2010. doi: 10.1021/jo7024477
16. [16]
  Q. Yan, J. Luo, D. Zhang-Negrerie, et al., J. Org. Chem. 76 (2011) 8690–8697. doi: 10.1021/jo2012187
17. [17]
  For a recent review: C. Chen, X. Wang, T. Yang, Front. Chem. 8 (2020) 551159.
18. [18]
  A. Parra, Chem. Rev. 119 (2019) 12033–12088. doi: 10.1021/acs.chemrev.9b00338
19. [19]
  W. Xiao, J. Wu, Chin. Chem. Lett. 32 (2021) 2751–2755. doi: 10.1016/j.cclet.2021.03.033
20. [20]
  C. Wang, X. Wang, D. Wang, et al., Chin. Chem. Lett. (2022), https://doi.org/10.1016/j.cclet.2022.03.055. doi: 10.1016/j.cclet.2022.03.055
21. [21]
  E.T. Pelkey, L. Chang, G.W. Gribble, Chem. Commun. (1996) 1909–1910.
22. [22]
  Y. Du, R. Liu, G. Linn, K. Zhao, Org. Lett. 8 (2006) 5919–5922. doi: 10.1021/ol062288o
23. [23]
  Y. Li, K. Ji, H. Wang, S. Ali, Y. Liang, J. Org. Chem. 76 (2011) 744–747. doi: 10.1021/jo1023014
24. [24]
  S. Ghosh, R. Nagarajan, RSC Adv. 4 (2014) 20136–20144. doi: 10.1039/C4RA02417F
25. [25]
  Z. Yang, T. Tian, Y. Du, et al., Chem. Commun. 53 (2017) 8050–8053. doi: 10.1039/C7CC03983B
26. [26]
  S. Badigenchala, V. Rajeshkumara, G. Sekar, Org. Biomol. Chem. 14 (2016) 2297–2305. doi: 10.1039/C5OB02449H
27. [27]
  J. Huang, Y. Yang, Z. Chen, Adv. Synth. Catal. 358 (2016) 201–206. doi: 10.1002/adsc.201500792
28. [28]
  Z. Tu, J. Tan, Z. Chen, T. Tu, Adv. Synth. Catal. 359 (2017) 4294–4299. doi: 10.1002/adsc.201700983
29. [29]
  L. Dai, J. Yuan, C. Wu, Z. Chen, Chem. Commun. 57 (2021) 4271–4274. doi: 10.1039/d1cc00846c
30. [30]
  H. Zhou, W. Chen, Z. Chen, Org. Lett. 20 (2018) 2590–2594. doi: 10.1021/acs.orglett.8b00776
31. [31]
  X. Chen, H. Zhou, Z. Chen, Org. Chem. Front. 6 (2019) 3415–3419. doi: 10.1039/c9qo00880b
32. [32]
  Z. Wang, L. Wei, Z. Cheng, J. Xia, Z. Chen, Chin. Chem. Lett. 32 (2021) 2756–2760. doi: 10.1016/j.cclet.2021.03.030
33. [33]
  H. Zhu, Z. Chen, Org. Lett. 18 (2016) 488–491. doi: 10.1021/acs.orglett.5b03533
34. [34]
  S. Rajasekar, P. Anbarasan, J. Org. Chem. 79 (2014) 8428–8434. doi: 10.1021/jo501043h
35. [35]
  J. Tian, K. Ng, J. Wong, T. Loh, Angew. Chem. Int. Ed. 51 (2012) 9105–9109. doi: 10.1002/anie.201204215
36. [36]
  M. Uyanik, D. Suzuki, T. Yasui, K. Ishihara, Angew. Chem. Int. Ed. 50 (2011) 5331–5334. doi: 10.1002/anie.201101522
37. [37]
  P. Finkbeiner, B. Nachtsheim, Synthesis 45 (2013) 979–999. doi: 10.1055/s-0032-1318330
1. [1]
  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
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]
  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
4. [4]
  Yan-Li Li , Zhi-Ming Li , Kai-Kai Wang , Xiao-Long He . Beyond 1,4-addition of in-situ generated (aza-)quinone methides and indole imine methides. Chinese Chemical Letters, 2024, 35(7): 109322-. doi: 10.1016/j.cclet.2023.109322
5. [5]
  Yunhao Zhang , Yinuo Wang , Siran Wang , Dazhen Xu . Progress in Selective Construction of Functional Aromatics from Nitrogenous Cycloalkanes. University Chemistry, 2024, 39(11): 136-145. doi: 10.3866/PKU.DXHX202401083
6. [6]
  Ping Sun , Yuanqin Huang , Shunhong Chen , Xining Ma , Zhaokai Yang , Jian Wu . Indole derivatives as agrochemicals: An overview. Chinese Chemical Letters, 2024, 35(7): 109005-. doi: 10.1016/j.cclet.2023.109005
7. [7]
  Yaping Zhang , Wei Zhou , Mingchun Gao , Tianqi Liu , Bingxin Liu , Chang-Hua Ding , Bin Xu . Oxidative cyclization of allyl compounds and isocyanide: A facile entry to polysubstituted 2-cyanopyrroles. Chinese Chemical Letters, 2024, 35(4): 108836-. doi: 10.1016/j.cclet.2023.108836
8. [8]
  Wenling Yuan , Fengli Li , Zhe Chen , Qiaoxin Xu , Zhenhua Guan , Nanyu Yao , Zhengxi Hu , Junjun Liu , Yuan Zhou , Ying Ye , Yonghui Zhang . AbnI: An α-ketoglutarate-dependent dioxygenase involved in brassicicene CH functionalization and ring system rearrangement. Chinese Chemical Letters, 2024, 35(5): 108788-. doi: 10.1016/j.cclet.2023.108788
9. [9]
  Junhua Wang , Xin Lian , Xichuan Cao , Qiao Zhao , Baiyan Li , Xian-He Bu . Dual polarization strategy to enhance CH₄ uptake in covalent organic frameworks for coal-bed methane purification. Chinese Chemical Letters, 2024, 35(8): 109180-. doi: 10.1016/j.cclet.2023.109180
10. [10]
  Xiangyu Chen , Aihao Xu , Dong Wei , Fang Huang , Junjie Ma , Huibing He , Jing Xu . Atomic cerium-doped CuO_x catalysts for efficient electrocatalytic CO₂ reduction to CH₄. Chinese Chemical Letters, 2025, 36(1): 110175-. doi: 10.1016/j.cclet.2024.110175
11. [11]
  Shiyi WANG , Chaolong CHEN , Xiangjian KONG , Lansun ZHENG , Lasheng LONG . Polynuclear lanthanide compound [Ce₄^ⅢCe₆^Ⅳ(μ₃-O)₄(μ₄-O)₄(acac)₁₄(CH₃O)₆]·2CH₃OH for the hydroboration of amides to amine. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 88-96. doi: 10.11862/CJIC.20240342
12. [12]
  Xiuzheng Deng , Changhai Liu , Xiaotong Yan , Jingshan Fan , Qian Liang , Zhongyu Li . Carbon dots anchored NiAl-LDH@In₂O₃ hierarchical nanotubes for promoting selective CO₂ photoreduction into CH₄. Chinese Chemical Letters, 2024, 35(6): 108942-. doi: 10.1016/j.cclet.2023.108942
13. [13]
  Hui Li , Yanxing Qi , Jia Chen , Juanjuan Wang , Min Yang , Hongdeng Qiu . Synthesis of amine-pillar[5]arene porous adsorbent for adsorption of CO₂ and selectivity over N₂ and CH₄. Chinese Chemical Letters, 2024, 35(11): 109659-. doi: 10.1016/j.cclet.2024.109659
14. [14]
  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
15. [15]
  Wei Zhou , Xi Chen , Lin Lu , Xian-Rong Song , Mu-Jia Luo , Qiang Xiao . Recent advances in electrocatalytic generation of indole-derived radical cations and their applications in organic synthesis. Chinese Chemical Letters, 2024, 35(4): 108902-. doi: 10.1016/j.cclet.2023.108902
16. [16]
  Pengcheng Su , Shizheng Chen , Zhihong Yang , Ningning Zhong , Chenzi Jiang , Wanbin Li . Vapor-phase postsynthetic amination of hypercrosslinked polymers for efficient iodine capture. Chinese Chemical Letters, 2024, 35(9): 109357-. doi: 10.1016/j.cclet.2023.109357
17. [17]
  Yi-Fan Wang , Hao-Yun Yu , Hao Xu , Ya-Jie Wang , Xiaodi Yang , Yu-Hui Wang , Ping Tian , Guo-Qiang Lin . Rhodium(Ⅲ)-catalyzed diastereo- and enantioselective hydrosilylation/cyclization reaction of cyclohexadienone-tethered α, β-unsaturated aldehydes. Chinese Chemical Letters, 2024, 35(9): 109520-. doi: 10.1016/j.cclet.2024.109520
18. [18]
  Wen-Tao Ouyang , Jun Jiang , Yan-Fang Jiang , Ting Li , Yuan-Yuan Liu , Hong-Tao Ji , Li-Juan Ou , Wei-Min He . Sono-photocatalytic amination of quinoxalin-2(1H)-ones with aliphatic amines. Chinese Chemical Letters, 2024, 35(10): 110038-. doi: 10.1016/j.cclet.2024.110038
19. [19]
  Chong-Yang Shi , Jian-Xing Gong , Zhen Li , Chao Shu , Long-Wu Ye , Qing Sun , Bo Zhou , Xin-Qi Zhu . Gold-catalyzed intermolecular amination of allyl azides with ynamides: Efficient construction of 3-azabicyclo[3.1.0] scaffold. Chinese Chemical Letters, 2025, 36(2): 109895-. doi: 10.1016/j.cclet.2024.109895
20. [20]
  Wen-Jing Li , Jun-Bo Wang , Yu-Heng Liu , Mo Zhang , Zhan-Hui Zhang . Molybdenum-doped carbon nitride as an efficient heterogeneous catalyst for direct amination of nitroarenes with arylboronic acids. Chinese Chemical Letters, 2025, 36(3): 110001-. doi: 10.1016/j.cclet.2024.110001

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(567)
HTML views(46)

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

I2/PhI(OAc)2-assisted oxidative CH amination protocols toward metal-free pragmatic synthesis of pyrrolo[2, 3-b]indoles

Metrics

通讯作者: 陈斌, bchen63@163.com

I₂/PhI(OAc)₂-assisted oxidative CH amination protocols toward metal-free pragmatic synthesis of pyrrolo[2, 3-b]indoles