Please do not adjust margins
ChemComm
Page 4 of 4
COMMUNICATION
Journal Name
Petrini, Chem. Rev. 2014, 114, 7108–D7O14I:910. .(1e0)39G/D. 0BCaCrt0o0l1i7,8RC.
Dalpozzo and M. Nardi, Chem. Soc. Rev. 2014, 43, 4728–
4750. (f) M. Shiri, Chem. Rev. 2012, 112, 3508–3549. (g) M.
Platon, R. Amardeil, L. Djakovitch and J.-C. Hierso, Chem. Soc.
Rev. 2012, 41, 3929–3968. (h) G. W. Gribble and J. C.
Badenock, Heterocyclic Scaffolds II: Reactions and
Applications of Indoles, Springer, Berlin, 2010.
Selected examples:(a) X. Qiu, P. Wang, D. Wang, M. Wang,
Y. Yuan and Z. Shi, Angew. Chem., Int. Ed. 2019, 58, 1504–
1508. (b) Y. Yang, P. Gao, Y. Zhao and Z. Shi, Angew. Chem.,
Int. Ed. 2017, 56, 3966–3971. (c) Y. Yang, R. Li, Y. Zhao, D.
Zhao and Z. Shi, J. Am. Chem. Soc. 2016, 138, 8734–8737. (d)
Y. Yang, X. Qiu, Y. Zhao, Y. Mu and Z. Shi, J. Am. Chem. Soc.
2016, 138, 495–498 (e) R. Dalpozzo, Chem. Soc. Rev. 2015,
44, 742-778. (f) S. Cacchi and G. Fabrizi, Chem. Rev. 2011,
111, 215–283.
Z. Chai, Y-M. Zhu, P-J. Yang, S. Wang, S. Wang, Z. Liu and G.
Yang, J. Am. Chem. Soc. 2015, 137, 10088−10091.
J. E. Spangler and H. M. L. Davies, J. Am. Chem. Soc. 2013,
135, 6802–6805.
K. Liu, S. Tang, P. Huang and A. Lei, Nat. Commun. 2017, 8,
775.
(a) H. S. Kim, Y. B. Kim, C. J. Lee, J. Y. Shin, J. G. La, T. H. Kim
and Y. M. Baek, KR 2015119653, 2015. (b) H.-F. Chen, M. J.
Su, Z. Q. Ji, J.-Y. Tsai, J. Brooks and P. M. Lahti,
US 20180375037, 2018. (c) J. U. Sim, S. J. Park and J. S. Jang,
KR 2016041676, 2016.
followed by deprotonations forms the para C–H amination product
1aa.11a Similarly, the SEO of 1aa results in an aryl radical cation 1aa’,
which reacts with indole nucleophile (2a) in situ and affords the
coupling adduct 3aa-1. The subsequent intramolecular nucleophilic
addition of the amino group to the iminium motif of 3aa-1 forms
radical 3aa-2 via deprotonation. Finally, the desired product 3aa is
generated via aerobic copper-catalyzed SEO and deprotonation of
3aa-2 followed by dehyroaromatization of 3aa-3.
3
O2
H
N
Ph
Ph
Ph
Ph
2
[CuII] [CuI]
N
NHPh
[CuII]/O2
- e
N
NHPh
Ph
Ph
1a
-2e, -2H+
1aa'
1aa
N
N
H
H
N
- H+
2a
Ph
Ph
Ph
N
N
N
NH
Ph
Ph
4
5
6
7
Ph
3aa-2
3aa-1
O2
Ph
Ph
N
[CuII]/O2
- e, - H+
[CuII] [CuI]
N
Ph
Ph
N
N
-2e, -2H+
N
N
3aa-3
Ph
3aa
Ph
Scheme 5 Plausible reaction pathways.
8
9
Y. Sawada, M. Hotta and M. Matsumoto, WO 2012050002,
2012.
(a) W. Wu, Y. Liu and D. Zhu, Chem Soc Rev. 2010, 39, 1489–
1502. (b) W. Jiang, Y. Li and Z. Wang, Chem Soc Rev. 2013, 42,
6113–6127.
In summary, through a new aerobic copper-catalyzed [3 + 2]
annulation reaction of diarylamines and indoles, we have
developed
a
straightforward synthesis of novel 2-
diarylaminoindolo[2,3-b]indoles with structural diversity. The
developed chemistry proceeds with the striking features broad
substrates, good functional tolerance, high chemo-selectivity,
excellent step and atom-efficiency, and no need for pre-installation
of specific coupling agents, the use of naturally abundant Cu/O2
catalyst system, which offers a practical platform for diverse
synthesis of the desired products that are difficult to prepare with
the conventional approaches. The developed chemistry is expected
to spur others to consctruct valuable N-heterocycles via single
electron oxidation induced C-H functionalization, and discover new
functioanl products including optoelectronic materials.
We thank the National Key Research and Development Program
of China (2016YFA0602900), National Natural Science Foundation of
China (21971071), and the foundation of the Department of
Education of Guangdong Province (2017KZDXM085). for financial
support.
10 (a) B. Cheng, B. Zu, Y. T. Li, S. X. Zhai, W. Xu, Y. Li and H. B.
Zhai, Adv. Synth. Catal. 2018, 360, 474–478. (b) S.
Badigenchala, V. Rajeshkumar and G. Sekar, Org. Biomol.
Chem. 2016, 14, 2297–2305. (c) K. Saito, P. K. Chikkade, M.
Kanai and Y. Kuninobu, Chem. Eur. J. 2015, 21, 8365–8368.
(d) H. Gao, Q.-L. Xu, M. Yousufuddin, D. H. Ess and L. Krti,
Angew. Chem., Int. Ed. 2014, 53, 2701–2705. (e) B. Prasad, B.
Y. Sreenivas, D. Rambabu, G. R. Krishna, C. M. Reddy, K. L.
Kumar and M. Pal, Chem. Commun. 2013, 49, 3970–3972. (f)
A. H. Jackson, D. N. Johnston and P. V. R. Shannon, J. Chem.
Soc. Chem. Commun. 1975, 22, 911–912.
11 (a) T. Liang, Z. Tan, H. Zhao, X. Chen, H. Jiang and M. Zhang,
ACS Catal. 2018, 8, 2242–2246. (b) T. Liang, H. Zhao, L. Gong,
H. Jiang and M. Zhang, iScience 2019, 15, 127–135. (c) F. Xie,
G. Lu, R. Xie, Q. Chen, H. Jiang and M. Zhang, ACS Catal. 2019,
9, 2718–2724. (d) Z. Tan, Y. Liang, J. Yang, L. Cao, H. Jiang and
M. Zhang, Org. Lett. 2018, 20, 6554–6558. (e) X.-W. Chen, H.
Zhao, C.-L. Chen, H.-F. Jiang and M. Zhang, Angew. Chem., Int.
Ed. 2017, 56, 14232–14236. (f) Y. T. Liang, H. F. Jiang, Z. D.
Tan, M. Zhang, Chem. Commun. 2018, 54, 10096–10099.
12 W. Li, W. P. Liu, D. K. Leonard, J. Rabeah, K. Junge, A.
Brückner and M. Beller, Angew. Chem., Int. Ed. 2019, 58,
10693–10697.
Conflicts of interest
There are no conflicts to declare.
13 (a) C. S. Wang, P. H. Pierre and J. F. Soule, Chem. Rev. 2019,
118, 7532–7585. (b) Z. Z. Wang, Q. Liu, X. C. Ji, G. J. Deng and
H. W. Huang, ACS Catal. 2020, 10, 154–159. (c) Z. H. Qu, F.
Zhang, G. J. Deng, H. W. Huang, Org. Lett. 2019, 21, 8239–
243. (d) F. Teng and J. Cheng, Chin. J. Chem. 2017, 35, 289–
298. (e) F. Teng, S. Song, Y. Jiang, J. T. Yu and J. Cheng, Chem.
Commun. 2015, 51, 5902–5905.
Notes and references
1
2
(a) Z. Xu, Q. Wang and J. Zhu, Chem. Soc. Rev. 2018, 47,
7882–7898. (b) E. Stempel and T. Gaich, Acc. Chem. Res.
2016, 49, 2390–2402. (c) W. Zi, Z. Zuo and D. Ma, Acc. Chem.
Res. 2015, 48, 702–711. (d) A. J. Kochanowska-Karamyan and
M. T. Hamann, Chem. Rev. 2010, 110, 4489–4497.
(a) A. A. Festa, L. G. Voskressensky and E. V. Van der Eycken,
Chem. Soc. Rev. 2019, 48, 4401–4423. (b) K. Nagaraju and D.
Ma, Chem. Soc. Rev. 2018, 47, 8018–8029. (c) J. Bariwal, L. G.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins