Citation: Tongyu Bi, Yi Xu, Xin Xu, Bixi Tang, Qing Yang, Yi Zang, Zhenyang Lin, Jia Li, Weibo Yang. Natural scaffolds-inspired synthesis of CF₃-substituted macrolides enabled by Rh-catalyzed C-H alkylation macrocyclization[J]. Chinese Chemical Letters, ;2022, 33(4): 2015-2020. doi: 10.1016/j.cclet.2021.10.043 shu

Natural scaffolds-inspired synthesis of CF₃-substituted macrolides enabled by Rh-catalyzed C-H alkylation macrocyclization

Tongyu Bi ^{a, b, 1} ,
Yi Xu ^{a, b, 1} ,
Xin Xu ^c ,
Bixi Tang ^{a, b} ,
Qing Yang ^{a, b} ,
Yi Zang ^{a, b} ,
Zhenyang Lin ^{c, *} ,
Jia Li ^{a, b, d, e, *} ,
Weibo Yang ^{a, b, d, *}

a.
Chinese Academy of Sciences Key Laboratory of Receptor Research, Shanghai Institute of Materia Medica (SIMM), Chinese Academy of Sciences, Shanghai 201203, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China
c.
Department of Chemistry, The Hong Kong University of Science and Technology, Hong Kong, China
d.
School of Pharmaceutical Science and Technology, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China
e.
Open Studio for Druggability Research of Marine Natural Products, Pilot National Laboratory for Marine Science and Technology (Qingdao), Qingdao 266237, China

chzlin@ust.hk

jli@simm.ac.cn

yweibo@simm.ac.cn

Received Date: 17 July 2021
Revised Date: 15 October 2021
Accepted Date: 18 October 2021
Available Online: 24 October 2021

Figures(7)

The development of innovative strategies and methods to provide natural product-like macrocycles not accessible by biosynthesis, but endowed with novel bioactivities and simplified structure, is highly desirable. Inspired by the key scaffolds of rapamycin and FR252921, herein, we report a Rh(Ⅲ)-catalyzed C-H alkylation macrocyclization, which enables access to CF₃-substituted macrolides. DFT calculations reveal that the chemoselectivity between C-H alkylation and olefination macrocyclization was highly controllable. Moreover, the unique CF₃-substituted macrolides showed potent anti-inflammation activities against TNF-α, IL-6 and CCL2 mRNA expression.
- Rh-catalyzed,
- C-H alkylation,
- Late stage macrocyclization,
- DFT calculation,
- Anti-inflammation
1. [1]
  F. Begnini, V. Poongavanam, B. Over, et al., J. Med. Chem. 64(2021) 1054-1072. doi: 10.1021/acs.jmedchem.0c01569
2. [2]
  E.M. Driggers, S.P. Hale, J. Lee, N.K. Terrett, Nat. Rev. Drug Discov. 7(2008) 608-624. doi: 10.1038/nrd2590
3. [3]
  E. Marsault, M.L. Peterson, J. Med. Chem. 54(2011) 1961-2004. doi: 10.1021/jm1012374
4. [4]
  J. Mallinson, I. Collins, Future Med. Chem. 4(2012) 1409-1438. doi: 10.4155/fmc.12.93
5. [5]
  S. Peña, L. Scarone, G. Serra, Future Med. Chem. 7(2015) 355-382. doi: 10.4155/fmc.14.133
6. [6]
  P.G. D. ougherty, Z. Qian, D. Pei, Biochem. J. 474(2017) 1109-1125. doi: 10.1042/BCJ20160619
7. [7]
  Z. Guo, S.Y. H. ong, J. Wang, et al., Nat. Chem. 11(2019) 254-263. doi: 10.1038/s41557-018-0187-4
8. [8]
  S.N. Sehgal, H. Baker, C. Vezina, J. Antibiot. 28(1975) 727-732. doi: 10.7164/antibiotics.28.727
9. [9]
  J. Heitman, N.R. Movva, M.N. Hall, Science 253(1991) 905-909. doi: 10.1126/science.1715094
10. [10]
  H. Tanaka, A. Kuroda, H. Marusawa, et al., J. Am. Chem. Soc. 109(1987) 5031-5033. doi: 10.1021/ja00250a050
11. [11]
  M.W. Harding, A. Galat, D.E. Uehling, S.L. Schreiber, Nature 341(1989) 758-760. doi: 10.1038/341758a0
12. [12]
  J.J. Siekierka, S.H. Hung, M. Poe, C.S. Lin, N.H. Sigal, Nature 341(1989) 755-757. doi: 10.1038/341755a0
13. [13]
  J. Liu, J.D. Farmer Jr, W.S. Lane, et al., Cell 66(1991) 807-815. doi: 10.1016/0092-8674(91)90124-H
14. [14]
  Z. Guo, Z. Cheng, J. Wang, et al., Angew. Chem. Int. Ed. 58(2019) 17158-17162. doi: 10.1002/anie.201905578
15. [15]
  C.S. Higman, J.A.M. Lummiss, D.E. Fogg, Angew. Chem. Int. Ed. 55(2016) 3552-3565. doi: 10.1002/anie.201506846
16. [16]
  C.W. Lee, R.H. Grubbs, J. Org. Chem. 66(2001) 7155-7158. doi: 10.1021/jo0158480
17. [17]
  M. Yu, S. Lou, F. Gonzalez-Bobes, Org. Process Res. Dev. 22(2018) 918-946. doi: 10.1021/acs.oprd.8b00093
18. [18]
  A. Gradillas, J. Pérez-Castells, Angew. Chem. Int. Ed. 45(2006) 6086-6101. doi: 10.1002/anie.200600641
19. [19]
  X. Yu, D. Sun, Molecules 18(2013) 6230-6268. doi: 10.3390/molecules18066230
20. [20]
  Y.H. Lau, P. de Andrade, Y. Wu, D.R. Spring, Chem. Soc. Rev. 44(2015) 91-102. doi: 10.1039/C4CS00246F
21. [21]
  I. Saridakis, N. Maulide Kaiser, ACS Cent. Sci. 6(2020) 1869-1889. doi: 10.1021/acscentsci.0c00599
22. [22]
  K.T. Mortensen, T.J. Osberger, T.A. King, H.F. Sore, D.R. Spring, Chem. Rev. 119(2019) 10288-10317. doi: 10.1021/acs.chemrev.9b00084
23. [23]
  D.G. Rivera, G.M. Ojeda-Carralero, L. Reguera, E.V. Van der Eycken, Chem. Soc. Rev. 49(2020) 2039-02059. doi: 10.1039/C9CS00366E
24. [24]
  S. Sengupta, G. Mehta, Org. Biomol. Chem. 18(2020) 1851-1876. doi: 10.1039/C9OB02765C
25. [25]
  H. Dong, C. Limberakis, S. Liras, D. Price, K. James, Chem. Commun. 48(2012) 11644-11646. doi: 10.1039/c2cc36962a
26. [26]
  L. Mendive-Tapia, S. Preciado, J. Garcia, et al., Nat. Commun. 6(2015) 7160. doi: 10.1038/ncomms8160
27. [27]
  Q. Bai, Z. Bai, H. Wang, Org. Lett. 21(2019) 8225-8228. doi: 10.1021/acs.orglett.9b02945
28. [28]
  A.F. Noisier, J. Garcia, I.A. Ionut, F. Albericio, Angew. Chem. Int. Ed. 56(2017) 314-318. doi: 10.1002/anie.201608648
29. [29]
  X. Zhang, G. Lu, M. Sun, et al., Nat. Chem. 10(2018) 540-548. doi: 10.1038/s41557-018-0006-y
30. [30]
  B. Li, X. Li, B. Han, et al., J. Am. Chem. Soc. 141(2019) 9401-9407. doi: 10.1021/jacs.9b04221
31. [31]
  X. Li, L. Qi, B. Li, et al., Org. Lett. 22(2020) 6209-6213. doi: 10.1021/acs.orglett.0c02342
32. [32]
  B. Han, B. Li, L. Qi, et al., Org. Lett. 22(2020) 6879-6883. doi: 10.1021/acs.orglett.0c02422
33. [33]
  Z. Ruan, N. Sauermann, E. Manoni, L. Ackermann, Angew. Chem. Int. Ed. 56(2017) 3172-3176. doi: 10.1002/anie.201611118
34. [34]
  N. Kaplaneris, F. Kaltenhäuser, G. Sirvinskaite, et al., Sci. Adv. 7(2021) eabe6202. doi: 10.1126/sciadv.abe6202
35. [35]
  A. Abula, Z. Xu, Z. Zhu, et al., J. Chem. Inf. Model. 60(2020) 6242-6250. doi: 10.1021/acs.jcim.0c00898
36. [36]
  A. Dal Pozzo, M. Ni, L. Muzi, et al., J. Med. Chem. 49(2006) 1808-1817. doi: 10.1021/jm0511334
37. [37]
  B. Jiang, M. Zhao, S.S. Li, Y.H. Xu, T.P. Loh, Angew. Chem. Int. Ed. 57(2018) 555-559. doi: 10.1002/anie.201710601
38. [38]
  Z. Bai, C. Cai, Z. Yu, H. Wang, Angew. Chem. Int. Ed. 57(2018) 13912-13916. doi: 10.1002/anie.201807953
39. [39]
  J. Tang, H. Chen, Y. He, et al., Nat. Commun. 9(2018) 3383. doi: 10.1038/s41467-018-05440-w
40. [40]
  M. Maraswami, J. Goh, T.P. Loh, Org. Lett. 22(2020) 9724-9728. doi: 10.1021/acs.orglett.0c03801
41. [41]
  Z. Bai, C. Cai, W. Sheng, Y. Ren, H. Wang, Angew. Chem. Int. Ed. 59(2020) 14686-14692. doi: 10.1002/anie.202007226
42. [42]
  S. Liu, C. Cai, Z. Bai, et al., Org. Lett. 23(2021) 2933-2937. doi: 10.1021/acs.orglett.1c00580
43. [43]
  L. Chen, H. Quan, Z. Xu, et al., Nat. Commun. 11(2020) 2151. doi: 10.1038/s41467-020-16084-0
44. [44]
  B. Song, P. Xie, Y. Li, et al., J. Am. Chem. Soc. 142(2020) 9982-9992. doi: 10.1021/jacs.0c00078
45. [45]
  J. Hao, X. Guo, S. He, et al., Nat. Commun. 12(2021) 1304. doi: 10.1038/s41467-021-21484-x
46. [46]
  G. Caron, V. Digiesi, S. Solaro, G. Ermondi, Drug Discov. Today 25(2020) 621-627. doi: 10.1016/j.drudis.2020.01.012
47. [47]
  Y. Chen, G. Coussanes, C. Souris, et al., J. Am. Chem. Soc. 141(2019) 13772-13777. doi: 10.1021/jacs.9b07185
48. [48]
  K. Fujine, M. Tanaka, K. Ohsumi, et al., J. Antibiot. 56(2003) 55-61. doi: 10.7164/antibiotics.56.55
49. [49]
  K. Fujine, F. Abe, N. Seki, et al., J. Antibiot. 56(2003) 62-67. doi: 10.7164/antibiotics.56.62
50. [50]
  K. Fujine, H. Ueda, M. Hino, T. Fujii, J. Antibiot. 56(2003) 68-71. doi: 10.7164/antibiotics.56.68
51. [51]
  M. Locati, G. Curtale, A. Mantovani, Annu. Rev. Pathol. 15(2020) 123-147. doi: 10.1146/annurev-pathmechdis-012418-012718
52. [52]
  H.L. Caslin, M. Bhanot, W.R. Bolus, A.H. Hasty, Immunol. Rev. 295(2020) 101-113. doi: 10.1111/imr.12853
53. [53]
  S.I. G. rivennikov, M. Karin, Ann. Rheum. Dis. 70(2011) i104-i108. doi: 10.1136/ard.2010.140145
1. [1]
  Jing Wang , Zhongliao Wang , Jinfeng Zhang , Kai Dai . Single-layer crystalline triazine-based organic framework photocatalysts with different linking groups for H2O2 production. Chinese Journal of Structural Chemistry, 2023, 42(12): 100202-100202. doi: 10.1016/j.cjsc.2023.100202
2. [2]
  Dan-Ying Xing , Xiao-Dan Zhao , Chuan-Shu He , Bo Lai . Kinetic study and DFT calculation on the tetracycline abatement by peracetic acid. Chinese Chemical Letters, 2024, 35(9): 109436-. doi: 10.1016/j.cclet.2023.109436
3. [3]
  Haibin Yang , Duowen Ma , Yang Li , Qinghe Zhao , Feng Pan , Shisheng Zheng , Zirui Lou . Mo doped Ru-based cluster to promote alkaline hydrogen evolution with ultra-low Ru loading. Chinese Journal of Structural Chemistry, 2023, 42(11): 100031-100031. doi: 10.1016/j.cjsc.2023.100031
4. [4]
  Xiaoyao Ma , Jinling Zhang , Ge Fang , He Gao , Jie Gao , Li Fu , Yuanyuan Hou , Gang Bai . Förster resonance energy transfer reveals phillygenin and swertiamarin concurrently target AKT on different binding domains to increase the anti-inflammatory effect. Chinese Chemical Letters, 2024, 35(5): 108823-. doi: 10.1016/j.cclet.2023.108823
5. [5]
  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
6. [6]
  Xiaoliu Liang , Chunliu Huang , Hui Liu , Hu Chen , Jiabao Shou , Hongwei Cheng , Gang Liu . Natural hydrogel dressings in wound care: Design, advances, and perspectives. Chinese Chemical Letters, 2024, 35(10): 109442-. doi: 10.1016/j.cclet.2023.109442
7. [7]
  Linshan Peng , Qihang Peng , Tianxiang Jin , Zhirong Liu , Yong Qian . Highly efficient capture of thorium ion by citric acid-modified chitosan gels from aqueous solution. Chinese Chemical Letters, 2024, 35(5): 108891-. doi: 10.1016/j.cclet.2023.108891
8. [8]
  Ya-Nan Yang , Zi-Sheng Li , Sourav Mondal , Lei Qiao , Cui-Cui Wang , Wen-Juan Tian , Zhong-Ming Sun , John E. McGrady . Metal-metal bonds in Zintl clusters: Synthesis, structure and bonding in [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–. Chinese Chemical Letters, 2024, 35(8): 109048-. doi: 10.1016/j.cclet.2023.109048
9. [9]
  Guangchang Yang , Shenglong Yang , Jinlian Yu , Yishun Xie , Chunlei Tan , Feiyan Lai , Qianqian Jin , Hongqiang Wang , Xiaohui Zhang . Regulating local chemical environment in O3-type layered sodium oxides by dual-site Mg²⁺/B³⁺ substitution achieves durable and high-rate cathode. Chinese Chemical Letters, 2024, 35(9): 109722-. doi: 10.1016/j.cclet.2024.109722
10. [10]
  Lian Sun , Honglei Wang , Ming Ma , Tingting Cao , Leilei Zhang , Xingui Zhou . Shape and composition evolution of Pt and Pt₃M nanocrystals under HCl chemical etching. Chinese Chemical Letters, 2024, 35(9): 109188-. doi: 10.1016/j.cclet.2023.109188
11. [11]
  Ruonan Yang , Jiajia Li , Dongmei Zhang , Xiuqi Zhang , Xia Li , Han Yu , Zhanhu Guo , Chuanxin Hou , Gang Lian , Feng Dang . Grain-refining Co_0.85Se@CNT cathode catalyst with promoted Li₂O₂ growth kinetics for lithium-oxygen batteries. Chinese Chemical Letters, 2024, 35(12): 109595-. doi: 10.1016/j.cclet.2024.109595
12. [12]
  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
13. [13]
  Yanan Zhou , Li Sheng , Lanlan Chen , Wenhua Zhang , Jinlong Yang . Axial coordinated iron-nitrogen-carbon as efficient electrocatalysts for hydrogen evolution and oxygen redox reactions. Chinese Chemical Letters, 2025, 36(1): 109588-. doi: 10.1016/j.cclet.2024.109588
14. [14]
  Chunyan Yang , Qiuyu Rong , Fengyin Shi , Menghan Cao , Guie Li , Yanjun Xin , Wen Zhang , Guangshan Zhang . Rationally designed S-scheme heterojunction of BiOCl/g-C₃N₄ for photodegradation of sulfamerazine: Mechanism insights, degradation pathways and DFT calculation. Chinese Chemical Letters, 2024, 35(12): 109767-. doi: 10.1016/j.cclet.2024.109767
15. [15]
  Pengfei Zhang , Qingxue Ma , Zhiwei Jiang , Xiaohua Xu , Zhong Jin . Transition-metal-catalyzed remote meta-C—H alkylation and alkynylation of aryl sulfonic acids enabled by an indolyl template. Chinese Chemical Letters, 2024, 35(8): 109361-. doi: 10.1016/j.cclet.2023.109361
16. [16]
  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
17. [17]
  Qian Huang , Zhaowei Li , Jianing Zhao , Ao Yu . Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon. University Chemistry, 2024, 39(3): 395-400. doi: 10.3866/PKU.DXHX202309018
18. [18]
  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
19. [19]
  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
20. [20]
  Jian Han , Li-Li Zeng , Qin-Yu Fei , Yan-Xiang Ge , Rong-Hui Huang , Fen-Er Chen . Recent advances in remote C(sp³)–H functionalization via chelating group-assisted metal-catalyzed chain-walking reaction. Chinese Chemical Letters, 2024, 35(11): 109647-. doi: 10.1016/j.cclet.2024.109647

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(623)
HTML views(58)

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

Natural scaffolds-inspired synthesis of CF3-substituted macrolides enabled by Rh-catalyzed C-H alkylation macrocyclization

Metrics

通讯作者: 陈斌, bchen63@163.com

Natural scaffolds-inspired synthesis of CF₃-substituted macrolides enabled by Rh-catalyzed C-H alkylation macrocyclization