Please do not adjust margins
ChemComm
Page 4 of 5
DOI: 10.1039/C7CC04748G
COMMUNICATION
Journal Name
Zhu, Chem. - Eur. J., 2013, 19, 14039; c) W. Kong, M.
Casimiro, E. Merino, and C. Nevado, J. Am. Chem. Soc., 2013,
135, 14480; d) L. Li, M. Deng, S.-C. Zheng, Y.-P. Xiong, B. Tan,
and X.-Y. Liu, Org. Lett., 2014, 16, 504; e) F. Yang, P. Klumphu,
in the Supporting Information). Interestingly, CF3-containing
tricyclic compound 9ba was obtained in 85% yield as a single
diastereoisomer after alcoholysis and nucleophilic attack
(Scheme 5). Moreover, functionalized aziridines 10ba and
11ba were obtained in 94% yield and 1:1 dr value under
LiAlH4-reduction conditions (For the details, see Scheme S3 in
Y.-M. Liang, and B. H. Lipshutz, Chem. Commun., 2014, 50
,
936; f) W. Fu, F. Xu, Y. Fu, C. Xu, S. Li, and D. Zou, Eur. J. Org.
Chem., 2014, 709.
9
a) B. Zhang, C. Mück-Lichtenfeld, C. G. Daniliuc, and A. Studer,
Angew. Chem., Int. Ed., 2013, 52, 10792; b) W. Kong, N.
Fuentes, A. García-Domínguez, E. Merino, and C. Nevado,
Angew. Chem., Int. Ed., 2013, 52, 13086.
the Supporting Information). Furthermore, products 9ba
10ba and 11ba were confirmed by X-ray analysis.20
,
In summary, we have developed a simple and convenient
copper-catalyzed consecutive trifluoromethylazidation and
rearrangement of aniline-linked 1,7-enynes with less reactive
Togni reagent I, providing facile access to structurally diverse
and valuable CF3-substituted azaspirocyclic dihydroquinolin-
2-ones. The reaction exhibits excellent diastereoselectivity,
good isolated yield and a broad substrate scope. Moreover,
the obtained azaspirocyclic products could be further
transformed into synthetically useful furoindoline derivatives
and other interesting multi-functionalized aziridine
compounds. All the new compounds have been well
identified by X-ray diffraction. Further investigations on
expanding the scope and applications of this method are
undergoing in our laboratory.
10 a) H. Egami, R. Shimizu, S. Kawamura, and M. Sodeoka,
Angew. Chem., Int. Ed., 2013, 52, 4000; b) N. Fuentes, W.
Kong, L. Fernández-Sánchez, E. Merino, and C. Nevado, J.
Am. Chem. Soc., 2015, 137, 964; c) L. Huang, J.-S. Lin, B. Tan,
and X.-Y. Liu, ACS Catal. 2015, 5, 2826; d) H.-L. Hua, Y.-T. He,
Y.-F. Qiu, Y.-X. Li, B. Song, P. Gao, X.-R. Song, D.-H. Guo, X.-Y.
Liu, and Y.-M. Liang, Chem. - Eur. J., 2015, 21, 1468; e) L.
Huang, L. Ye, X.-H. Li, Z.-L. Li, J.-S. Lin, and X.-Y. Liu, Org. Lett.,
2016, 18, 5284; f) Z.-L. Li, X.-H. Li, N. Wang, N.-Y. Yang, and
X.-Y. Liu, Angew. Chem., Int. Ed., 2016, 55, 15100;
11 a) X. Dong, R. Sang, Q. Wang, X.-Y. Tang, and M. Shi, Chem. -
Eur. J., 2013, 19, 16910; b) Z.-Z. Zhu, K. Chen, L.-Z. Yu, X.-Y.
Tang, and M. Shi, Org. Lett., 2015, 17, 5994; c) L.-Z. Yu, Q. Xu,
X.-Y. Tang, and M. Shi, ACS Catal., 2016, 6, 526.
12 a) F. Wang, X. Qi, Z. Liang, P. Chen, and G. Liu, Angew. Chem.,
Int. Ed., 2014, 53, 1881; b) F. Wang, N. Zhu, P. Chen, J. Ye,
and G. Liu, Angew. Chem., Int. Ed., 2015, 54, 9356; c) N. Zhu,
F. Wang, P. Chen, J. Ye, and G. Liu, Org. Lett., 2015, 17, 3580.
13 L.-Z. Yu, Y. Wei, and M. Shi, Chem. Commun., 2016, 52
13163
14 a) Y.-T. He, L.-H. Li, Z.-Z. Zhou, H.-L. Hua, Y.-F. Qiu, X.-Y. Liu,
and Y.-M. Liang, Org. Lett., 2014, 16, 3896.
15 The crystal data of 2aa and 2ba have been deposited in CCDC
with number 1494648 and 1535602, respectively.
We are grateful for the financial support from the National
Basic Research Program of China (973)-2015CB856603, the
National Natural Science Foundation of China (20472096,
21372241, 21572052, 20672127, 21421091, 21372250,
21121062, 21302203, and 20732008), and the Fundamental
Research Funds for the Central Universities 222201717003.
,
Notes and references
16 The crystal data of
5
number 1501511,
have been deposited in CCDC with
and the reaction of
1
a) W.-W. Peng, G.-Z. Zeng, W.-W. Song, and N.-H. Tan, Chem.
Biodiversity, 2013, 10, 1317; b) M. Schlosser, Angew. Chem.,
Int. Ed., 2006, 45, 5432; c) I. Mierina, M. Jure, and A. Stikute,
Chem. Heterocycl. Comp., 2016, 52, 509.
a) C.-Y. An, X.-M. Li, H. Luo, C.-S. Li, M.-H. Wang, G.-M. Xu,
and B.-G. Wang, J. Nat. Prod., 2013, 76, 1896; b) M. Chen, C.-
trifluoromethylazidation of 1,6-enyne with Togni reagent has
been reported by Liang’s group: Y.-T. He, Q. Wang, J. Zhao,
X.-Z. Wang, Y.-F. Qiu, Y.-C. Yang, J.-Y. Hu, X.-Y. Liu, and Y.-M.
Liang, Adv. Synth. Catal., 2015, 357, 3069.
2
L. Shao, Z.-G. She, and C.-Y. Wang, J. Nat. Prod., 2014, 77
2720.
,
3
4
R. Uchida, R. Imasato, H. Tomoda, and S. Omura, J. Antibiot.,
2006, 59, 652.
a) C. Liu, W. Zhang, L.-X. Dai, and S.-L. You, Org. Lett., 2012,
14, 4525; b) C. Liu, Q. Yin, L.-X. Dai, and S.-L. You, Chem.
Commun., 2015, 51, 5971; c) Y.-N. Wang, T.-R. Li, M.-M.
Zhang, B.-Y. Cheng, L.-Q. Lu, and W.-J. Xiao, J. Org. Chem.,
2016, 81, 10491; d) V. Bizet, G. M. Borrajo-Calleja, C. Besnard,
17 The product 7bl has been reported by Wan’s group: Y. Zhao,
Y. Hu, H. Wang, X. Li, and B. Wan, J. Org. Chem., 2016, 81,
4412. A similar report was also seen: X.-H. Ouyang, R.-J. Song,
Y. Liu, M. Hu, and J.-H. Li, Org. Lett., 2015, 17, 6038.
and C. Mazet, ACS Catal., 2016, 6, 7183.
5
6
a) M. Shimizu, and T. Hiyama, Angew. Chem., Int. Ed., 2005,
44, 214; b) K. Müller, C. Faeh, and F. Diederich, Science, 2007,
317, 1881.
For selected reviews of trifluoromethylation of organic
compounds, see: a) A. Studer, Angew. Chem., Int. Ed., 2012,
51, 8950; b) H. Liu, Z. Gu, and X. Jiang, Adv. Synth. Catal.,
2013, 355, 617; c) H. Egami, and M. Sodeoka, Angew. Chem.,
Int. Ed., 2014, 53, 8294; d) E. Merino, and C. Nevado, Chem.
Soc. Rev., 2014, 43, 6598; e) J. Charpentier, N. Früh, and A.
Togni, Chem. Rev., 2015, 115, 650; f) C. Ni, M. Hu, and J. Hu,
Chem. Rev., 2015, 115, 765; g) C. Alonso, E. M. de Marigorta,
G. Rubiales, and F. Palacios, Chem. Rev., 2015, 115, 1847.
X. Mu, T. Wu, H.-Y. Wang, Y.-L. Guo, and G. Liu, J. Am. Chem.
Soc., 2012, 134, 878.
18 The crystal data of 7aa have been deposited in CCDC with
number 1535603.
19 The crystal data of 8bf have been deposited in CCDC with
number 1549550.
20 The crystal data of 9ba, 10ba, and 11ba have been deposited
in CCDC with number 1553802, 1552058, and 1554196.
7
8
a) H. Egami, R. Shimizu, and M. Sodeoka, J. Fluorine Chem.,
2013, 152, 51; b) P. Xu, J. Xie, Q. Xue, C. Pan, Y. Cheng, and C.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins