10.1002/anie.202004719
Angewandte Chemie International Edition
COMMUNICATION
Y. Meng, J. X. Li, Y. W. Zheng, C. Ye, Z. J. Li, B. Chen, C. H. Tung, L. Z.
Wu. Chem. Eur. J. 2015, 21, 18080–18084; n) K. H. He, F. F. Tan, C. Z.
Zhou, G. J. Zhou, X. L. Yang, Y. Li. Angew. Chem. Int. Ed. 2017, 56,
3080–3084; o) W. Cao, C. Wu, T. Lei, X. Yang, B. Chen, C. Tung, L. Wu,
Chin. J. Catal. 2018, 39, 1194–1201.
education exchange, for graduate fellowships. We thank Mr.
Brent Billett for checking the experimental procedure, Mr. Carlo
Berti for preparing some testing substrates, Dr. Jun Zhu for
conducting control experiments, and Prof. Weixin Tang for UV-Vis
spectroscopy.
[11] For a catalyst-free direct photochemical annulation of special styrene-
type substrates, see: J. Zhang, X. Zhang, T. Wang, X. Yao, P. Wang, P.
Wang, S. Jing, Y. Liang, Z. Zhang. J. Org. Chem. 2017, 82, 12097-12105.
[12] a) G. E. Dobereiner, R. H. Crabtree. Chem. Rev. 2010, 110, 681–703; b)
Momirlan, M.; Veziroglu, T. N. Int. J. Hydrogen Energy 2005, 30, 795–
802; d) Sartbaeva, A.; Kuznetsov, V. L.; Wells, S. A.; Edwards, P. P.
Energy Environ. Sci. 2008, 1, 79; e) Armaroli, N.; Balzani, V.
ChemSusChem 2011, 4, 21; f) Gunanathan, G.; Milstein, D. Science
2013, 341, 1229712; g) A. C. Marr. Catal. Sci. Technol. 2012, 2, 279–
287.
Keywords: cyclodehydrogenation • cobaloxime catalysis •
polyaromatic hydrocarbons • photochemical reaction • Scholl
reaction
[1]
a) J. Löwe. Z. Chemie, 1868, 4, 603–604; b) A. T. Balaban, C. D.
Nenitzescu in Friedel-Crafts and Related Reactions, vol. 2 (Eds: G. A.
Olah), Wiley, New York, 1964, pp. 979–1047. For reviews on Scholl
reaction, see; c) M. Grzybowski, K. Skonieczny, H. Butenschoen, D. T.
Gryko, Angew. Chem. Int. Ed., 2013, 52, 9900-9930.
[13] T. J. Cuppen, W. H. Laarhoven. J. Am. Chem. Soc. 1972, 94, 5914-5915.
[14] J. G. West, D. Huang, E. J. Sorensen. Nat. Commun, 2015, 6, 10093.
[15] F. B. Mallory, C. S. Wood. J. Org. Chem. 1964, 29, 3374-3377.
[16] A. Yamamoto, Y. Matsui, T. Asada, M. Kumeda, K. Takagi, Y. Suenaga,
N. Nagae, E. Ohta, H. Sato, S. Koseki, H. Naito, H. Ikeda. J. Org. Chem.
2016, 81, 3168−3176.
[2]
For recent reviews of synthesis of PAHs, see: a) D. Pérez, E. Guitián.
Chem. Soc. Rev. 2004, 33, 274-283. (b) K. Y. Yoon, G. Dong. Mater.
Chem. Front. 2020, 4, 29-45. (c) A. Jolly, D. Miao, M. Daigle, J. F. Morin.
Angew. Chem. Int. Ed. 2020, 59, 4624–4633. (d) B. P. Mathew, M. R.
Kuram. Inorg. Chim. Acta. 2019, 490, 112–129. (e) Y. Segawa, T.
Maekawa, K. Itami. Angew. Chem. Int. Ed. 2015, 54, 66-81.
[17] T. Sato, S. Shimada, K. Hata. Bull. Chem. Soc. Jpn. 1971, 44, 2484-2490.
[18] W. Q. Liu, T. Lei, S. Zhou, X. L. Yang, J. Li, B. Chen, J. Sivaguru, C. H.
Tung, L. Z. Wu. J. Am. Chem. Soc. 2019, 141, 13941–13947.
[19] N. P. Schepp and L. J. Johnston. J. Am. Chem. Soc. 1996, 118, 2872-
2881.
[3]
a) B. T. King, J. Kroulík, C. R. Robertson, P. Rempala, C. L. Hilton, J. D.
Korinek, L. M. Gortari. J. Org. Chem. 2007, 72, 2279-2288; b) X. Dou, X.
Yang, G. J. Bodwell, M. Wagner, V. Enkelmann, K. Müllen. Org. Lett.
2007, 9, 2485-2488.
[20] pKa values of hydrocarbon radical cation are known to be very low (in
DMSO, for example, toluene’s pKa (C–H•+)
dihydroanthracene’s pKa (C–H•+) –24). Thus, CoI-mediated
= –23 and 9,10-
[4]
[5]
[6]
S. Fujimoto, K. Matsumoto, M. Shindo. Adv. Synth. Catal. 2016, 358,
3057-3061.
=
deprotonation from II (Figure 1) or 1,4-dihydronaphthalene radical cation
(Scheme 2C) is feasible. BDE of hydrocarbon radical cation are known
to be very low too. For references of pKa/BDE values of hydrocarbon
radical cations: a) X. Zhang, F. G. Bordwell. J. Org. Chem. 1992, 57,
4163-4168; b) X. S. Xue, P. Ji, B. Zhou, J. P. Cheng. Chem. Rev. 2017,
117, 8622−8648.
P. Röse, S. Emge, C. A. König, G. Hilt. Adv. Synth. Catal. 2017, 359,
1359-1372.
a) L. Liu, B. Yang, T. J. Katz, M. K. Poindexter. J. Org. Chem. 1991, 56,
3769-3775; b) K. B. Jørgensen, Molecules 2010, 15, 4334–4358; c) F. B.
Mallory, C. W. Mallory. Org. React. 1984, 30, 1-456.
[7]
a) M. Shimizu, I. Nagao, Y. Tomioka, T. Kadowaki, T. Hiyama.
Tetrahedron 2011, 67, 8014-8026; b) J. Tu, G. Li, X. Zhao, F. Xu.
Tetrahedron Lett. 2019, 60, 44-47; c) K. Murayama, Y. Sawada, K.
Noguchi, K. Tanaka. J. Org. Chem. 2013, 78, 6202-6210; d) T. T.
Jayanth, C. H. Cheng, Chem. Commun. 2006, 8, 894-896; e) M. Iwasaki,
Y. Araki, S. Iino, Y. Nishihara. J. Org. Chem. 2015, 80, 9247-9263.
For H-OMe eliminative photocyclization, see; a) R. G. Giles, M. V.
Sargent. J. Chem. Soc., Perkin Trans. 1, 1974, 2447–2450. For H-Cl
eliminative photocyclization, see; b) M. Daigle, A. Picard-Lafond, E.
Soligo, J. F. Morin. Angew. Chem. Int. Ed. 2016, 55, 2042–2047. For H-
F eliminative photocyclization, see: c) O. Allemann, S, Duttwyler, P.
Romanato, K. K. Baldridge, J. S. Siegel. Science, 2011, 332, 574–577;
d) K. Y. Amsharov, P. Merz. J. Org. Chem, 2012, 77, 5445–5448.
For recent reviews, see: a) J. L. Dempsey, B. S. Brunschwig, J. R.
Winkler, H. B. Gray. Acc. Chem. Res. 2009, 42, 1995–2004; b) N. Kaeffer,
M. Chavarot-Kerlidou, V. Artero. Acc. Chem. Res. 2015, 48, 1286–1295.
[21] T. H. Chao, J. H. Espenson. J. Am. Chem. Soc. 1978, 100, 129-133.
[22] Using this method to prepare nanographenes was unfruitful under the
current reaction conditions primarily due to the solubility issue of the
substrate in MeCN.
[8]
[9]
[10] For selected examples, see: a) Y. W. Zheng, B. Chen, P. Ye, K. Feng,
W. Wang, Q. Y. Meng, L. Z. Wu, C. H. Tung. J. Am. Chem. Soc. 2016,
138, 10080-10083; b) Q. Yang, L. Zhang, C. Ye, S. Luo, L. Z. Wu, C. H.
Tung. Angew. Chem. Int. Ed. 2017, 56, 3694–3698; c) X. W. Gao, Q. Y.
Meng, J. X. Li, J. J. Zhong, T. Lei, X. B. Li, C. H. Tung, L. Z. Wu. ACS
Catal. 2015, 5, 2391–2396; d) X. Hu, G. Zhang, F. Bu, A. Lei. Angew.
Chem. Int. Ed. 2018, 57, 1286–1290; e) F. Zhao, Q. Yang, J. Zhang, W.
Shi, H. Hu, F. Liang, W. Wei, S. Zhou. Org. Lett. 2018, 20, 7753–7757;
f) H. Yi, L. Niu, C. Song, Y. Li, B. Dou, A. K. Singh, A. Lei. Angew. Chem.
Int. Ed. 2017, 56, 1120–1124; g) L. Niu, H. Yi, S. Wang, T. Liu, J. Liu, A.
Lei. Nat. Commun. 2017, 8, 14226. h) G. Zhang, Y. Lin, X. Luo, X. Hu,
C. Chen, A. Lei. Nat. Commun. 2018, 9, 1225; i) G. Zhang, C. Liu, H. Yi,
Q. Meng, C. Bian, H. Chen, J. X. Jian, L. Z. Wu, A. Lei, J. Am. Chem.
Soc. 2015, 137, 9273–9280; j) J. J. Zhong, Q. Y. Meng, B. Liu, X. B. Li,
X. W. Gao, T. Lei, C. J. Wu, Z. J. Li, C. H. Tung, L. Z. Wu. Org. Lett. 2014,
16, 1988–1991; k) G. Zhang, X. Hu, C. W. Chiang, H. Yi, P. Pei, A. K.
Singh, A. Lei, J. Am. Chem. Soc. 2016, 138, 12037–12040; l) C. J. Wu,
Q. Y. Meng, T. Lei, J. J. Zhong, W. Q. Liu, L. M. Zhao, Z. J. Li, B. Chen,
C. H. Tung, L. Z. Wu. ACS Catal. 2016, 6, 4635–4639; m) M. Xiang, Q.
4
This article is protected by copyright. All rights reserved.