Citation: Jingyao Geng, Zhang Fang, Guangliang Tu, Yingsheng Zhao. Non-directed highly para-selective CH functionalization of TIPS-protected phenols promoted by a carboxylic acid ligand[J]. Chinese Chemical Letters, ;2023, 34(3): 107609. doi: 10.1016/j.cclet.2022.06.032 shu

Non-directed highly para-selective CH functionalization of TIPS-protected phenols promoted by a carboxylic acid ligand

Jingyao Geng ^a ,
Zhang Fang ^a ,
Guangliang Tu ^a ,
Yingsheng Zhao ^{a, b, *,}

a.
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
b.
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453000, China

yszhao@suda.edu.cn

Received Date: 15 April 2022
Revised Date: 7 June 2022
Accepted Date: 12 June 2022
Available Online: 16 June 2022

Figures(8)

Palladium-catalyzed non-directed CH functionalization provides an efficient approach for direct functionalization of arenes, but it usually suffers from poor site selectivity, limiting its wide application. Herein, it is reported for the first time that the carboxylic acid ligand of 3, 5-dimethyladamantane-1-carboxylic acid (1-DMAdCO₂H) can affect the site selectivity during the CH activation step in palladium-catalyzed non-directed CH functionalization, leading to highly para-selective CH olefination of TIPS-protected phenols. This transformation displayed good generality in realizing various other para-selective CH functionalization reactions such as halogenation, and allylation reactions. A wide variety of phenol derivatives including bioactive molecules of triclosan, thymol, and propofol, were compatible substrates, leading to the corresponding para-selective products in moderate to good yields. A preliminary mechanism study revealed that the spatial repulsion factor between carboxylic acid ligand and bulky protecting group resulted in the selective CH activation at the less sterically hindered para-position. This new model non-directed para-selective CH functionalization can provide a straightforward route for remote site-selective CH activations.
- para-Selective,
- Non-directed,
- CH olefination
1. [1]
  H.X. Dai, G. Li, X.G. Zhang, A.F. Stepan, J.Q. Yu, J. Am. Chem. Soc. 135 (2013) 7567–7571. doi: 10.1021/ja400659s
2. [2]
  L. Wan, N. Dastbaravardeh, J.Q. Yu, J. Am. Chem. Soc. 135 (2013) 18056–18059. doi: 10.1021/ja410760f
3. [3]
  S. Lee, K.L. Tan, J. Am. Chem. Soc. 135 (2013) 18778–18781. doi: 10.1021/ja4107034
4. [4]
  L. Campeau, K. Fagnou, J. Am. Chem. Soc. 126 (2004) 9186–9187. doi: 10.1021/ja049017y
5. [5]
  L. Chu, M. Shang, K. Tanaka, Q. Chen, J.Q. Yu, ACS Cent. Sci. 1 (2015) 394–399. doi: 10.1021/acscentsci.5b00312
6. [6]
  M.T. Mihai, G.R. Genov, R.J. Phipps, Chem. Soc. Rev. 47 (2018) 149–171. doi: 10.1039/C7CS00637C
7. [7]
  J. Xu, J. Chen, J.Q. Yu, J. Am. Chem. Soc. 141 (2019) 1903–1907. doi: 10.1021/jacs.8b13403
8. [8]
  G. Meng, N.Y.S. Lam, E.L. Lucas, et al., J. Am. Chem. Soc. 142 (2020) 10571–10591. doi: 10.1021/jacs.0c04074
9. [9]
  S. Porey, X. Zhang, S. Bhowmick, V.K. Singh, D. Maiti, J. Am. Chem. Soc. 142 (2020) 3762–3774. doi: 10.1021/jacs.9b10646
10. [10]
  S. Bag, T. Patra, A. Modak, D. Maiti, J. Am. Chem. Soc. 137 (2015) 11888–11891. doi: 10.1021/jacs.5b06793
11. [11]
  T. Patra, S. Bag, A. Modak, D. Maiti, Angew. Chem. Int. Ed. 55 (2016) 7751–7755. doi: 10.1002/anie.201601999
12. [12]
  P. Wang, P. Verma, J.Q. Yu, Nature551 (2017) 589–593.
13. [13]
  Z. Zhang, K. Tanaka, J.Q. Yu, Nature543 (2017) 538–543. doi: 10.1038/nature21418
14. [14]
  P. Wedi, M. Gemmeren, Angew. Chem. Int. Ed. 57 (2018) 13016–13027. doi: 10.1002/anie.201804727
15. [15]
  H. Chen, P. Wedi, M. Gemmeren, Angew. Chem. Int. Ed. 130 (2018) 2523–2527. doi: 10.1002/ange.201712235
16. [16]
  K. Naksomboon, C. Valderas, M. Gomez-Martinez, M.A. Fernandez-Ibanez, ACS Catal. 7 (2017) 6342–6346. doi: 10.1021/acscatal.7b02356
17. [17]
  N. Kuhl, J. Wencel-Delord, F. Glorius, Angew. Chem. Int. Ed. 51 (2012) 10236–10254. doi: 10.1002/anie.201203269
18. [18]
  S. Kancherla, K.B. Jorgensen, M.A. Fernandez-Ibanez, Synthesis51 (2019) 643–663. doi: 10.1055/s-0037-1610852
19. [19]
  Y. Kuninobu, H. Ida, M. Nishi, M. Kanai, Nat. Chem. 7 (2015) 712–717. doi: 10.1038/nchem.2322
20. [20]
  Y. Saito, Y. Segawa, K. Itami, J. Am. Chem. Soc. 137 (2015) 5193–5198. doi: 10.1021/jacs.5b02052
21. [21]
  H.J. Davis, M.T. Mihai, R.J. Phipps, J. Am. Chem. Soc. 138 (2016) 12759–12762. doi: 10.1021/jacs.6b08164
22. [22]
  M.T. Mihai, B.J. Williams, R.J. Phipps, J. Am. Chem. Soc. 141 (2019) 15477–15482. doi: 10.1021/jacs.9b07267
23. [23]
  K. Naksomboon, J. Poater, F.M. Bickelhaupt, M.A. Fernandez-Ibanez, J. Am. Chem. Soc. 141 (2019) 6719–6725. doi: 10.1021/jacs.9b01908
24. [24]
  W.L. Jia, N. Westerveld, K.M. Wong, T. Morsch, M.A. Fernandez-Ibanez, Org. Lett. 21 (2019) 9339–9342. doi: 10.1021/acs.orglett.9b03505
25. [25]
  P. Wang, P. Verma, J.Q. Yu, Nature551 (2017) 489–493. doi: 10.1038/nature24632
26. [26]
  L.C. Campeau, S. Rousseaux, K. Fagnou, J. Am. Chem. Soc. 127 (2005) 18020–18021. doi: 10.1021/ja056800x
27. [27]
  M. Lafrance, C.N. Rowley, K. Fagnou, J. Am. Chem. Soc. 128 (2006) 8754–8756. doi: 10.1021/ja062509l
28. [28]
  D.R. Stuart, K. Fagnou, Science316 (2007) 1172–1175. doi: 10.1126/science.1141956
29. [29]
  G. Tu, C. Yuan, Y. Li, J. Zhang, Y. Zhao, Angew. Chem. Int. Ed. 57 (2018) 15597–15601. doi: 10.1002/anie.201809788
30. [30]
  W.T. Fan, Y. Li, D. Wang, S.J. Ji, Y. Zhao, J. Am. Chem. Soc. 142 (2020) 20524–20530. doi: 10.1021/jacs.0c09545
31. [31]
  Y. Jiang, B. Li, N. Ma, et al., Angew. Chem. Int. Ed. 60 (2021) 19030–19034. doi: 10.1002/anie.202105631
32. [32]
  M. Dams, S. Celen, P.A. Jacobs, Angew. Chem. Int. Ed. 42 (2003) 3512–3515. doi: 10.1002/anie.200351524
33. [33]
  B. Yin, M. Fu, Q. Zhu, Chem. Commun. 56 (2020) 3293–3296. doi: 10.1039/d0cc00940g
34. [34]
  H.T. Kim, E. Kang, J. Joo, Org. Lett. 23 (2021) 3657–3662. doi: 10.1021/acs.orglett.1c01040
35. [35]
  V. Sukowski, W.L. Jia, R. Diest, M.A. Fernandez-Ibanez, Eur. J. Org. Chem. 2021 (2021) 4132–4135. doi: 10.1002/ejoc.202100737
36. [36]
  T. Fujihara, A. Yoshida, M. Satou, Y. Tsuji, Catal. Commun. (2016) 71–74.
37. [37]
  Q. Sun, H. Zhang, Q. Wang, G. Chen, Angew. Chem. Int. Ed. 60 (2021) 19620–19625. doi: 10.1002/anie.202104430
38. [38]
  D. Mu, F. Gao, G. Chen, G. He, ACS Catal. 7 (2017) 1880–1885. doi: 10.1021/acscatal.6b03661
39. [39]
  Y. Tanji, N. Mitsutake, Y. Tsuji, Angew. Chem. Int. Ed. 57 (2018) 10314–10317. doi: 10.1002/anie.201804566
40. [40]
  Y. Tanji, Y. Tsuji, T, Fujihara. Chem. Commun. 56 (2020) 3843–3846. doi: 10.1039/d0cc01129k
41. [41]
  C.C. Piras, D.K. Smith, Angew. Chem. Int. Ed. 59 (2020) 853–859. doi: 10.1002/anie.201911404
42. [42]
  G. Hamasaka, D. Roy, A. Tazawa, Y. Uozumi, ACS Catal. 9 (2019) 11640–11646. doi: 10.1021/acscatal.9b04593
43. [43]
  F. Liu, C. Liu, S. Dai, Green Chem. 18 (2016) 6536–6544. doi: 10.1039/C6GC02237E
44. [44]
  B. Wang, H.X. Sun, B. Chena, Z.H. Sun, Green Chem. 11 (2009) 1112–1114. doi: 10.1039/b905443j
45. [45]
  D. Willcox, G.N. Chappell, F.K. Hogg, M.J. Gaunt, Science345 (2016) 851–857. doi: 10.1126/science.aaf9621
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