Y. Shi, X. Yu, C.-Y. Li
SHORT COMMUNICATION
[2]
[3]
S. Chuprakov, F. W. Hwang, V. Gevorgyan, Angew. Chem. Int.
Ed. 2007, 46, 4757; Angew. Chem. 2007, 119, 4841.
a) E. J. Yoo, M. Ahlquist, S. H. Kim, I. Bae, V. V. Fokin, K. B.
Sharpless, S. Chang, Angew. Chem. Int. Ed. 2007, 46, 1730;
Angew. Chem. 2007, 119, 1760; b) J. Raushel, V. V. Fokin, Org.
Lett. 2010, 12, 4952; c) Y. Liu, X. Wang, J. Xu, Q. Zhang, Y.
Zhao, Y. Hu, Tetrahedron 2011, 67, 6294.
sponding α-amino ketone (see the Supporting Information
for more details). On the basis of the above experiments, we
believe both pathways are possible and that the mechanism
depends on the relative reactivity of the different functional
groups.
[4]
[5]
T. Horneff, S. Chuprakov, N. Chernyak, V. Gevorgyan, V. V.
Fokin, J. Am. Chem. Soc. 2008, 130, 14972.
For recent publications, see: a) T. Miura, Y. Funakoshi, M.
Murakami, J. Am. Chem. Soc. 2014, 136, 2272; b) S. W. Kwok,
L. Zhang, N. P. Grimster, V. V. Fokin, Angew. Chem. Int. Ed.
2014, 53, 3452; Angew. Chem. 2014, 126, 3520; c) H. Shang, Y.
Wang, Y. Tian, J. Feng, Y. Tang, Angew. Chem. Int. Ed. 2014,
53, 5662; Angew. Chem. 2014, 126, 5768; d) K. Chen, Z.-Z.
Zhu, Y.-S. Zhang, X.-Y. Tang, M. Shi, Angew. Chem. Int. Ed.
2014, 53, 6645; Angew. Chem. 2014, 126, 6763; e) E. E. Schultz,
V. N. G. Lindsay, R. Sarpong, Angew. Chem. Int. Ed. 2014, 53,
9904; Angew. Chem. 2014, 126, 10062; f) Y. Shi, A. V. Gulevich,
V. Gevorgyan, Angew. Chem. Int. Ed. 2014, 53, 14191; Angew.
Chem. 2014, 126, 14415; g) S. Kim, J. Mo, J. Kim, T. Ryu, P. H.
Lee, Asian J. Org. Chem. 2014, 3, 926; h) C.-E. Kim, S. Park,
D. Eom, B. Seo, P. H. Lee, Org. Lett. 2014, 16, 1900; i) X.-J.
Ma, S.-F. Pan, H.-X. Wang, W.-Z. Chen, Org. Lett. 2014, 16,
4554; j) H. Shen, J. Fu, J. Gong, Z. Yang, Org. Lett. 2014, 16,
5588; k) J. Feng, Y. Wang, Q. Li, R. Jiang, Y. Tang, Tetrahedron
Lett. 2014, 55, 6455; l) Y. Tian, Y. Wang, H. Shang, X. Xu, Y.
Tang, Org. Biomol. Chem. 2015, 13, 612; m) Y.-S. Zhang, X.-
Y. Tang, M. Shi, Chem. Commun. 2014, 50, 15971; n) X.-Y.
Tang, Y.-S. Zhang, L. He, Y. Wei, M. Shi, Chem. Commun.
2015, 51, 133; o) H. Ding, S. Hong, N. Zhang, Tetrahedron
Lett. 2015, 56, 507; p) T. Ryu, Y. Baek, P. H. Lee, J. Org. Chem.
2015, 80, 2376; q) Y. Wang, X. Lei, Y. Tang, Chem. Commun.
2015, 51, 4507; r) Y.-Z. Zhao, H.-B. Yang, X.-Y. Tang, M. Shi,
Chem. Eur. J. 2015, 21, 3562; s) T. Miura, Y. Funakoshi, Y.
Fujimoto, J. Nakahashi, M. Murakami, Org. Lett. 2015, 17,
2454; t) E. Lee, T. Ryu, E. Shin, J.-Y. Son, W. Choi, P. H. Lee,
Org. Lett. 2015, 17, 2470.
Scheme 3. Proposed mechanism.
Conclusions
In summary, a novel protocol for the synthesis of 2,5-
epoxybenzo[f][1,4]oxazepines was developed. The compli-
cated ring system was constructed from readily available
starting materials in a one-pot procedure. Many valuable
functional groups were well tolerated in this transforma-
tion. Considering that 1,4-oxazepine derivatives are impor-
tant moieties in medicinal chemistry with a variety of bio-
logical activities,[15] this protocol may be applicable to the
synthesis of related compounds.
[6]
[7]
[8]
a) S. Chuprakov, S. W. Kwok, L. Zhang, L. Lercher, V. V. Folin,
J. Am. Chem. Soc. 2009, 131, 18034; b) N. Grimster, L. Zhang,
V. V. Fokin, J. Am. Chem. Soc. 2010, 132, 2510; c) Y. Xing, G.
Sheng, J. Wang, P. Lu, Y. Wang, Org. Lett. 2014, 16, 1244; d)
T. Miura, T. Nakamuro, C.-J. Liang, M. Murakami, J. Am.
Chem. Soc. 2014, 136, 15905.
a) T. Miura, Y. Funakoshi, M. Morimoto, T. Biyajima, M. Mu-
rakami, J. Am. Chem. Soc. 2012, 134, 17440; b) N. Selander,
B. T. Worrel, V. V. Fokin, Angew. Chem. Int. Ed. 2012, 51,
13054; Angew. Chem. 2012, 124, 13231; c) R. Liu, M. Zhang,
G. Winston-McPherson, W. Tang, Chem. Commun. 2013, 49,
4376.
a) S. Chuprakov, J. A. Malik, M. Zibinsky, V. V. Fokin, J. Am.
Chem. Soc. 2011, 133, 10352; b) J.-M. Yang, C.-Z. Zhu, X.-Y.
Tang, M. Shi, Angew. Chem. Int. Ed. 2014, 53, 5142; Angew.
Chem. 2014, 126, 5242; c) D. Yadagiri, P. Anbarasan, Org. Lett.
2014, 16, 2510; d) B. Rajagopal, C.-H. Chou, C.-C. Chung, P.-
C. Lin, Org. Lett. 2014, 16, 3752; e) J. S. Alford, H. M. L. Dav-
ies, J. Am. Chem. Soc. 2014, 136, 10266; f) S. Park, W.-S. Yong,
S. Kim, P. H. Lee, Org. Lett. 2014, 16, 4468; g) X. Ma, F. Wu,
X. Yi, H. Wang, W. Chen, Chem. Commun. 2015, 51, 6862.
Experimental Section
General Procedure: Under a nitrogen atmosphere, toluene (2.0 mL)
was added to a reaction flask charged with [Rh2(piv)4] (1.2 mg,
1 mol-%), 1-sulfonyl-1,2,3-triazole 2 (0.2 mmol), and o-hydroxy-
benzaldehyde derivative 1 (0.24 mmol) at room temperature. The
mixture was then stirred at 100 °C until TLC analysis showed that
the unstable intermediate was completely consumed. The mixture
was cooled to room temperature and was filtered through a short
plug of silica gel. The solution was concentrated and purified by
flash chromatography (petroleum ether/EtOAc, 20:1) to give corre-
sponding product 3.
Acknowledgments
This work was generously supported by the National Natural Sci-
ence Foundation of China (NSFC) (grant number 21372204),
Zhejiang Sci-Tech University 521 Project, and the Young Research-
ers Foundation of Zhejiang Provincial Top Key Academic Disci-
pline of Chemical Engineering and Technology, Zhejiang Sci-Tech
University (grant number ZYG2015004).
[9]
a) T. Miura, T. Biyajima, T. Fuji, M. Murakami, J. Am. Chem.
Soc. 2012, 134, 194; b) T. Miura, T. Tanaka, T. Biyajima, A.
Yada, M. Murakami, Angew. Chem. Int. Ed. 2013, 52, 3883;
Angew. Chem. 2013, 125, 3975; c) S. Chuprakov, B. T. Worrell,
N. Selander, R. K. Sit, V. V. Fokin, J. Am. Chem. Soc. 2014,
136, 195; d) H. J. Jeon, D. J. Jung, J. H. Kim, Y. Kim, J. Bouf-
fard, S. Lee, J. Org. Chem. 2014, 79, 9865; e) T. Miura, T.
Tanaka, K. Matsumoto, M. Murakami, Chem. Eur. J. 2014,
20, 16078; f) T. Miura, T. Nakamuro, K. Hiraga, M. Murak-
ami, Chem. Commun. 2014, 50, 10474; g) D. J. Lee, E. J. Yoo,
Org. Lett. 2015, 17, 1830.
[1] a) M. E. Hermes, F. D. Marsh, J. Am. Chem. Soc. 1967, 89,
4760; b) R. E. Harmon, F. Stanley Jr., S. K. Gupta, J. Johnson,
J. Org. Chem. 1970, 35, 3444.
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