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provide the desired product 3a and regenerate the CuCl catalyst.
In summary, we have demonstrated the first example of visible-
light-driven copper-catalyzed oxidative annulation of salicyl
hydrazones with wide range of commercially available terminal
alkynes, including aliphatic terminal alkynes, as starting substrates
without any need of external oxidants (organic oxidants) at room
temperature with complete regioselectivity. The reaction occurs
most probably via a unique base-promoted 6-endo-dig ring closure
process, photoredox initiated C=N double bond cleavage and N2
evolution. Also, we have observed that the desired products are
totally different from those obtained by thermal heating methods.
It is mainly due to the different reaction mechanisms, i.e.,
photoinduced electronic excitation-single electron transfer vs.
thermal heating induced nuclear vibrational excitation-bond
stretching/breaking/re-formation. As an additional benefit, this
efficient method gives the best synthetic route to prepare bioactive
molecules, such as MAO-B inhibitor and HRP-inhibitor at very mild
conditions without the need of hydroxy group pre-protection. The
current method can be readily scaled up to a preparative gram (1–2
g) scale. From a synthetic point of view, the current photoredox
method involving utilization of O2 as oxidant, inexpensive copper as
X. Zhang, P. Li and L. Wang, AdvD. SOyI:n1t0h..10C3a9t/aCl.92C0C1071,83051H9,
443; (e) J. Hou, A. Ee, W. Feng, J. Xu, Y. Zhao and J. Wu, J.
Am. Chem. Soc. 2018, 140, 5257.
10 H. Zeng & C.-J. Li, Angew. Chem. Int. Ed. 2014, 53, 13862.
11 (a) M. A. Tasdelen and Y. Yagci, Angew. Chem. Int. Ed.
2013, 52, 5930; (b) S. Paria and O. Reiser, Chem.Cat.
Chem., 2014, 6, 2477; (c) O. Reiser, Acc. Chem. Res.
2016, 49, 1990; (d) Q. M. Kainz, C. D. Matier, A.
Bartoszewicz, S. L. Zultanski, J. C. Peters and G. C. Fu,
Science 2016, 351, 681.
12 (a) A. Sagadevan and K. C. Hwang, Adv. Synth. Catal.
2012, 354, 3421; (b) A. Sagadevan, A. Ragupathi, C.-C. Lin,
J. R. Hwu and K. C. Hwang, Green Chem. 2015, 17, 1113;
(c) A. Ragupathi, A. Sagadevan, C.-C. Lin, J. R. Hwu and K.
C. Hwang, Chem. Commun. 2016, 52, 11756; (d) A.
Ragupathi, V. P. Charpe, A. Sagadevan, C.-C. Lin, J. R.
Hwu and K. C. Hwang, Adv. Synth. Catal. 2017, 359, 1138;
(e) A. Sagadevan, V. P. Charpe, A. Ragupathi, and K. C.
Hwang, J. Am. Chem. Soc. 2017, 139, 2896. (f) A.
Sagadevan, V. K. K. Kishore, and K. C. Hwang, Angew.
Chem. 2019, 58, 3838.
a
catalyst and low energy visible light for photo-excitation,
represents an extremely simple and an eco-friendly process for the
regioseletive synthesis of 3-arylcoumarins under very mild
conditions.
This work was supported by the Ministry of Science and
Technology, Taiwan.
13 (a)Y. F. Liang and N. Jiao, Acc. Chem. Res. 2017, 50, 1640;
(b) X. Li and N. Jiao, Chin. J. Chem. 2017, 35, 1349; (c) W.
Liang, Z. Zhang, D. Yi, Q. Fu, S. Chen, L. Yang, F. Du, J. Ji
and W. Wei, Chin. J. Chem. 2017, 35, 1378; (d) X. Huang,
X. Li, M. Zou, S. Song, C. Tang, Y. Yuan and N. Jiao, J. Am.
Chem. Soc. 2014, 136, 14858; (e) H. J. Zhang, A. W.
Schuppe, S.-T. Pan, J. X. Chen, B. R. Wang, T. R.
Newhouse, and L. Yin, J. Am. Chem. Soc. 2018, 140, 5300.
14 (a) Y. Xi and J. Wang, Chem. Soc. Rev., 2017, 46, 2306; (b)
Q. Xiao, Y. Xia, H. Li, Y. Zhang and J. Wang, Angew. Chem.
Int. Ed. 2011, 50, 1114; (c) L. Zhou, Y. Shi, Q. Xiao, Y. Liu,
F. Ye, Y. Zhang and J. Wang, Org.Lett. 2011, 13, 968; (d)
N. D. Paul, S. Mandal, M. Otte, X. Cui, X. P. Zhang and B.
de Bruin, J. Am. Chem. Soc. 2014, 136, 1090; (e) S. Mai
and Q. Song, Angew.Chem.Int.Ed.2017, 56, 7952; (f) Z.
Zhang, Q. Zhou, W. Yu, T. Li, Y. Zhang and J. Wang; Chin.
J. Chem. 2017, 35, 387; (g) W.-D, Chu, F. Guo, L. Yu, J.
Hong, Q. Liu, F. Mo, Y. Zhang and J. Wang, Chin. J.
Chem. 2018, 36, 217.
Notes and references
1
(a) R. O. Kennedy and R. D. Thornes, Coumarins: biology,
applications, and mode of action, John Wiley & Sons,
Chichester, New York, 1997; (b) S. J. Bullock, C. E. Felton,
R. V. Fennessy, L. P. Harding, M. Andrews, S. J. A. Pope, C.
R. Rice & T. RiisJohannessen, Dalton Trans., 2009, 10570.
(a) A. Murakami, G. Gao, M. Omura, M. Yano, C. Ito, H.
Furukawa, D. Takahashi, K. Koshimizu and H. Ohigashi,
Bioorg. Med. Chem. Lett. 2000, 10, 59; (b) C. Wang, C.
Wu, J. Zhu, R. H. Miller and Y. Wang, J. Med. Chem. 2011,
54, 2331; (c) S. Sandhu, Y. Bansal, O. Silakari and G.
Bansal, Bioorg. Med. Chem. 2014, 22, 3806.
2
3
(a) M. Matos, D. Vina, C. Picciau, F. Orallo, L. Santana
and E. Uriarte, Bioorg. Med. Chem. Lett., 2009, 19, 5053;
(b) N. Robledo-O'Ryan, M.J. Matos, S. Vazquez-Rodriguez,
L. Santana, E. Uriarte, M. Moncada-Basualto, F. Mura, M.
Lapier, J.D. Maya and C. Olea-Azar, Bioorg. Med. Chem.
2017, 25, 621.
15 F. Pina, M. J. Melo, C. A. T. Laia, J. Parola and J. C. Lima,
Chem. Soc. Rev. 2012, 41, 869.
16 M. Paya, B. Halliwell and J. R. Hoult. Biochem. Pharmacol.
1992, 44, 205.
17 See the Supporting Information. CCDC 1841164 (3a),
CCDC 1841166 (4f), CCDC 1841165 (4k) contain the
supplementary crystallographic data for this paper.
18 S. J. Blanksby & G. B. Ellison, Acc. Chem. Res. 2003, 36,
255.
19 S.-U. Kim, Y. Liu, K. M. Nash, J. L. Zweier, A. Rockenbauer
and F. A. Villamena, J. Am. Chem. Soc. 2010, 132, 17157.
20 (a) C. Bengtsson and F. Almqvist, J. Org. Chem. 2011, 76,
9817; (b) T.-Y. Ye, S. Manikandan and C.-M. Sun, Org.
Lett. 2017, 19, 3103.
4
5
6
H. Pechmann, Ber. Dtsch. Chem. Ges., 1884, 17, 929.
W. H. Perkin, J. Chem. Soc., 1868, 21, 181.
I. Yavari, R. Hekmat-Shoar and A. Zonouzi, Tetrahedron
Lett. 1998, 39, 2391.
7
8
E. Knoevenagel, Ber. Dtsch. Chem. Ges., 1904, 37, 4461.
(a) A. Unsinn, S. H. Wunderlich and P. Knochela, Adv.
Synth. Catal.,2013, 355, 989; (b) J. Liu, X. Zhang, L. Shi,
M. Liu, Y. Yue, F. Li and K. Zhuo, Chem. Commun., 2014,
50, 9887; (c) F. Jafarpour, M. Abbasnia, J. Org. Chem.,
2016, 81, 11982; (d) H. Tan, H. Li, J. Wang and L. Wang,
Chem. Eur. J. 2015, 21, 1904; (e) Z. Shi and C. He, J. Org.
Chem. 2004, 69, 3669.
21 K. K. Toh, Y.-F. Wang, E. P. J. Ng and S. Chiba, J. Am.
Chem. Soc., 2011, 133, 13942.
22 H. Wang, Y. Wang, D. Liang, L. Liu, J. Zhang and Q. Zhu,
Angew. Chem., Int. Ed., 2011, 50, 5678.
9
(a) U. Sharma, T. Naveen, A. Maji, S. Manna and D. Maiti,
Angew. Chem. Int. Ed. 2013, 52, 12669; (b) A. Seoane, N.
Casanova, N. QuiÇones, J. L. Mascarenas and M. Gulias,
J. Am. Chem. Soc. 2014, 136, 834; (c) Y. Yamamoto and N.
23 V. Shimizu & M. Kanai, Tetrahedron Lett. 2014, 55, 3727.
4 | J. Name., 2012, 00, 1-3
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