Citation: Min Yan, Zihao Ye, Ping Lu. Catalyst-free, visible-light-induced [2π + 2σ] cycloaddition towards azabicyclohexanes[J]. Chinese Chemical Letters, ;2025, 36(6): 110540. doi: 10.1016/j.cclet.2024.110540 shu

Catalyst-free, visible-light-induced [2π + 2σ] cycloaddition towards azabicyclohexanes

Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, Shanghai 200433, China

plu@fudan.edu.cn

Received Date: 31 May 2024
Revised Date: 20 September 2024
Accepted Date: 9 October 2024
Available Online: 12 October 2024

Figures(8)

2-Azabicyclo[2.1.1]hexanes (aza-BCHs) are constrained pyrrolidine analogues with improved physicochemical characteristics in drug design. Here, we report a direct visible light-mediated photocycloaddition of 4-aza-coumarins with mono- or disubstituted bicyclo[1.1.0]butanes for synthesizing aza-BCHs without an external catalyst. The introduction of the ester group on 4-azacoumarin is critical for direct imine excitation and versatile synthetic utility. Preliminary mechanistic studies indicated that the reaction took place primarily at the triplet hypersurface.
- Bicyclo[1.1.0]butane,
- Bioisosteres,
- Imine,
- Photochemistry,
- Spectroscopy
1. [1]
  F. Lovering, J. Bikker, C. Humblet, J. Med. Chem. 52 (2009) 6752–6756. doi: 10.1021/jm901241e
2. [2]
  M.A.M. Subbaiah, N.A. Meanwell, J. Med. Chem. 64 (2021) 14046–14128. doi: 10.1021/acs.jmedchem.1c01215
3. [3]
  P.K. Mykhailiuk, Org. Biomol. Chem. 17 (2019) 2839–2849. doi: 10.1039/c8ob02812e
4. [4]
  M.R. Bauer, P. Di Fruscia, S.C.C. Lucas, et al., RSC Med. Chem. 12 (2021) 448–471. doi: 10.1039/d0md00370k
5. [5]
  O.O. Grygorenko, D.M. Volochnyuk, B.V. Vashchenko, Eur. J. Org. Chem. (2021) 6478–6510. doi: 10.1002/ejoc.202100857
6. [6]
  P. Bellotti, F. Glorius, J. Am. Chem. Soc. 145 (2023) 20716–20732. doi: 10.1021/jacs.3c08206
7. [7]
  B.R. Shire, E.A. Anderson, JACS Au 3 (2023) 1539–1553. doi: 10.1021/jacsau.3c00014
8. [8]
  J.M. Anderson, N.D. Measom, J.A. Murphy, D.L. Poole, Angew. Chem. Int. Ed. 60 (2021) 24754–24769. doi: 10.1002/anie.202106352
9. [9]
  S. Cuadros, J. Paut, E. Anselmi, et al., Angew. Chem. Int. Ed. 63 (2024) e202317333. doi: 10.1002/anie.202317333
10. [10]
  R. Kleinmans, T. Pinkert, S. Dutta, et al., Nature 605 (2022) 477–482. doi: 10.1038/s41586-022-04636-x
11. [11]
  R. Guo, Y.C. Chang, L. Herter, et al., J. Am. Chem. Soc. 144 (2022) 7988–7994. doi: 10.1021/jacs.2c02976
12. [12]
  R. Kleinmans, S. Dutta, K. Ozols, et al., J. Am. Chem. Soc. 145 (2023) 12324–12332. doi: 10.1021/jacs.3c02961
13. [13]
  A. Denisenko, P. Garbuz, S.V. Shishkina, N.M. Voloshchuk, P.K. Mykhailiuk, Angew. Chem. Int. Ed. 59 (2020) 20515–20521. doi: 10.1002/anie.202004183
14. [14]
  S. Dutta, D. Lee, K. Ozols, et al., J. Am. Chem. Soc. 146 (2024) 2789–2797. doi: 10.1021/jacs.3c12894
15. [15]
  S. Dutta, Y. -L. Lu, J.E. Erchinger, et al., J. Am. Chem. Soc. 146 (2024) 5232–5241. doi: 10.1021/jacs.3c11563
16. [16]
  S. Agasti, F. Beltran, E. Pye, et al., Nat. Chem. 15 (2023) 535–541. doi: 10.1038/s41557-023-01135-y
17. [17]
  N. Radhoff, C.G. Daniliuc, A. Studer, Angew. Chem. Int. Ed. 62 (2023) e202304771. doi: 10.1002/anie.202304771
18. [18]
  L. Tang, Y. Xiao, F. Wu, et al., Angew. Chem. Int. Ed. 62 (2023) e202310066. doi: 10.1002/anie.202310066
19. [19]
  M. de Robichon, T. Kratz, F. Beyer, et al., J. Am. Chem. Soc. 145 (2023) 24466–24470.
20. [20]
  Q. Fu, S. Cao, J. Wang, et al., J. Am. Chem. Soc. 146 (2024) 8372–8380. doi: 10.1021/jacs.3c14077
21. [21]
  N. Frank, J. Nugent, B.R. Shire, et al., Nature 611 (2022) 721–726. doi: 10.1038/s41586-022-05290-z
22. [22]
  T. Yu, J. Yang, Z. Wang, et al., J. Am. Chem. Soc. 145 (2023) 4304–4310. doi: 10.1021/jacs.2c13740
23. [23]
  Y. Zheng, W. Huang, R.K. Dhungana, et al., J. Am. Chem. Soc. 144 (2022) 23685–23690. doi: 10.1021/jacs.2c11501
24. [24]
  T. Iida, J. Kanazawa, T. Matsunaga, et al., J. Am. Chem. Soc. 144 (2022) 21848–21852. doi: 10.1021/jacs.2c09733
25. [25]
  T.V.T. Nguyen, A. Bossonnet, M.D. Wodrich, J. Waser, J. Am. Chem. Soc. 145 (2023) 25411–25421. doi: 10.1021/jacs.3c09789
26. [26]
  J. Zhang, J.Y. Su, H. Zheng, H. Li, W.P. Deng, Angew. Chem. Int. Ed. 63 (2024) e202318476. doi: 10.1002/anie.202318476
27. [27]
  V.V. Levterov, O. Michurin, P.O. Borysko, et al., J. Org. Chem. 83 (2018) 14350–14361. doi: 10.1021/acs.joc.8b02071
28. [28]
  Y. Liang, R. Kleinmans, C.G. Daniliuc, F. Glorius, J. Am. Chem. Soc. 144 (2022) 20207–20213. doi: 10.1021/jacs.2c09248
29. [29]
  Y. Liang, F. Paulus, C.G. Daniliuc, F. Glorius, Angew. Chem. Int. Ed. 62 (2023) e202305043. doi: 10.1002/anie.202305043
30. [30]
  V.V. Levterov, Y. Panasyuk, V.O. Pivnytska, P.K. Mykhailiuk, Angew. Chem. Int. Ed. 59 (2020) 7161–7167. doi: 10.1002/anie.202000548
31. [31]
  A. Denisenko, P. Garbuz, N.M. Voloshchuk, et al., Nat. Chem. 15 (2023) 1155–1163. doi: 10.1038/s41557-023-01222-0
32. [32]
  P. Hughes, J. Clardy, J. Org. Chem. 53 (1988) 4793–4796. doi: 10.1021/jo00255a024
33. [33]
  G.R. Krow, Y.B. Lee, W.S. Lester, et al., J. Org. Chem. 63 (1998) 8558–8560. doi: 10.1021/jo9808472
34. [34]
  K. Dhake, K.J. Woelk, J. Becica, et al., Angew. Chem. Int. Ed. 61 (2022) e202204719. doi: 10.1002/anie.202204719
35. [35]
  M. Economidou, N. Mistry, K.M.P. Wheelhouse, D.M. Lindsay, Org. Process Res. Dev. 27 (2023) 1585–1615. doi: 10.1021/acs.oprd.3c00210
36. [36]
  C.E. Garrett, K. Prasad, Adv. Synth. Catal. 346 (2004) 889–900. doi: 10.1002/adsc.200404071
37. [37]
  C.B. Kelly, J.A. Milligan, L.J. Tilley, T.M. Sodano, Chem. Sci. 13 (2022) 11721–11737. doi: 10.1039/d2sc03948f
38. [38]
  M. Wang, Y. Huang, C. Li, P. Lu, Org. Chem. Front. 9 (2022) 2149–2153. doi: 10.1039/d2qo00167e
39. [39]
  M. Latrache, N. Hoffmann, Chem. Soc. Rev. 50 (2021) 7418–7435. doi: 10.1039/d1cs00196e
40. [40]
  A.D. Richardson, M.R. Becker, C.S. Schindler, Chem. Sci. 11 (2020) 7553–7561. doi: 10.1039/d0sc01017k
41. [41]
  S.K. Kandappa, L.K. Valloli, S. Ahuja, J. Parthiban, J. Sivaguru, Chem. Soc. Rev. 50 (2021) 1617–1641. doi: 10.1039/d0cs00717j
42. [42]
  E. Kumarasamy, S.K. Kandappa, R. Raghunathan, S. Jockusch, J. Sivaguru, Angew. Chem. Int. Ed. 56 (2017) 7056–7061. doi: 10.1002/anie.201702273
43. [43]
  R. Sakamoto, T. Inada, S. Sakurai, K. Maruoka, Org. Lett. 18 (2016) 6252–6255. doi: 10.1021/acs.orglett.6b03003
44. [44]
  M.R. Becker, E.R. Wearing, C.S. Schindler, Nat. Commun. 10 (2019) 5095. doi: 10.1038/s41467-019-13072-x
45. [45]
  D.M. Flores, M.L. Neville, V.A. Schmidt, Nat. Commun. 13 (2022) 2764. doi: 10.1038/s41467-022-30393-6
46. [46]
  T. Nishio, Y. Omote, J. Org. Chem. 50 (1985) 1370–1373. doi: 10.1021/jo00209a005
47. [47]
  T. Nishio, J. Org. Chem. 49 (1984) 827–832. doi: 10.1021/jo00179a015
48. [48]
  M.R. Becker, E.R. Wearing, C.S. Schindler, Nat. Chem. 12 (2020) 898–905. doi: 10.1038/s41557-020-0541-1
49. [49]
  X. Li, J. Großkopf, C. Jandl, T. Bach, Angew. Chem. Int. Ed. 60 (2021) 2684–2688. doi: 10.1002/anie.202013276
50. [50]
  W. Wang, M.K. Brown, Angew. Chem. Int. Ed. 62 (2023) e202305622. doi: 10.1002/anie.202305622
51. [51]
  K.A. Rykaczewski, M.R. Becker, M.J. Anantpur, et al., J. Am. Chem. Soc. 144 (2022) 19089–19096. doi: 10.1021/jacs.2c08191
52. [52]
  D.E. Blackmun, S.A. Chamness, C.S. Schindler, Org. Lett. 24 (2022) 3053–3057. doi: 10.1021/acs.orglett.2c01008
53. [53]
  J. Huang, T. -P. Zhou, N. Sun, et al., Nat. Commun. 15 (2024) 1431. doi: 10.1038/s41467-024-45687-0
54. [54]
  G.S. Hammond, J. Saltiel, A.A. Lamola, et al., J. Am. Chem. Soc. 86 (1964) 3197–3217. doi: 10.1021/ja01070a002
55. [55]
  N.G. Minnaard, E. Havinga, Recl. Trav. Chim. Pays-Bas 92 (1973) 1179–1188. doi: 10.1002/recl.19730921102
56. [56]
  W.G. Herkstroeter, J. Am. Chem. Soc. 97 (1975) 4161–4167. doi: 10.1021/ja00848a001
57. [57]
  S.V. Rosokha, J.K. Kochi, Acc. Chem. Res. 41 (2008) 641–653. doi: 10.1021/ar700256a
58. [58]
  E. Arceo, I.D. Jurberg, A. Álvarez-Fernández, P. Melchiorre, Nat. Chem. 5 (2013) 750–756. doi: 10.1038/nchem.1727
59. [59]
  O.L. Garry, M. Heilmann, J. Chen, et al., J. Am. Chem. Soc. 145 (2023) 3092–3100. doi: 10.1021/jacs.2c12163
60. [60]
  G. Huang, R. Guillot, C. Kouklovsky, B. Maryasin, A. de la Torre, Angew. Chem. Int. Ed. 61 (2022) e202208185. doi: 10.1002/anie.202208185
61. [61]
  A. Mizuno, S. Miura, M. Watanabe, et al., Org. Lett. 15 (2013) 1686–1689. doi: 10.1021/ol400469w
62. [62]
  P. Zhang, Y. Li, Z. Yan, J. Gong, Z. Yang, J. Org. Chem. 84 (2019)15958–15971. doi: 10.1021/acs.joc.9b02230
63. [63]
  K.E. Prosser, R.W. Stokes, S.M. Cohen, ACS Med. Chem. Lett. 11 (2020) 1292–1298. doi: 10.1021/acsmedchemlett.0c00121
64. [64]
  C. Isert, K. Atz, J. Jiménez-Luna, G. Schneider, Sci. Data 9 (2022) 273. doi: 10.1038/s41597-022-01390-7
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