Please do not adjust margins
Organic & Biomolecular Chemistry
Page 4 of 6
COMMUNICATION
Organic & Biomolecular Chemistry
2
3
O
O
DOI: 10.1039/D0OB02310H
O
N
O
N
O
O
O
Oxford, 2008.
H
1,3-H shift
O
(a) D. Bellocchi, A. Macchiarulo, G. Costantino and R.
Pellicciari, Bioorg. Med. Chem., 2005, 13, 1151; (b)
Vangrevelinghe, E.; Zimmermann, K.; Schoepfer, J.;
Portmann, R.; Fabbro, D.; Furet, P. J. Med. Chem., 2003, 46,
2656.
O
O
N
E
D
H
1a
[Cp*RhCl2]2
O
s
i
s
HCl
y
C-H
metalation
l
o
n
O
o
t
4
5
6
7
8
S. Patil, S. Kamath, T. Sanchez, N. Neamati, R. F. Schinazi and
J. K. Buolamwini, Bioorg. Med. Chem., 2007, 15, 1212.
R. Zeecheng, S. J. Yan and C. C. Cheng, J. Med. Chem., 1978,
21, 199.
M. Tang, S. I. Odejinmi, Y. M. Alette, H. Vankayalapati and K.
Lai, Bioorg. Med. Chem., 2011, 19, 588.
HCl
o
N
r
O
p
HO
O
O
N
O
O
F
Rh
N
Cl
Cp*
O
A
Cl
Rh
Cp*
O
O
e
n
H2O
e
n
o
O
O
b
N2
m
i
r
3aa
T. Ishioka, A. Tanatani, K. Nagasawa and Y. Hashimoto,
Bioorg. Med. Chem. Lett., 2003, 13, 2655.
t
i
a
g
a
i
r
c
-
h
n
a
s
m
t
e
r
o
o
r
r
O
R
t
y
f
C
i
o
2a
N
n
N2, Cl-
(a) L. V. Rompuy, N. Schamp, N. D. Kimpe and R. V. Parijs,
Tetrahedron Lett., 1974, 5, 2503; (b) J. E. Baldwin, R. M.
Adlington and D. J. Birch, Tetrahedron Lett., 1985, 26, 5931;
(c) J. E. Baldwin, R. M. Adlington and L. C. Mellor,
Tetrahedron, 1994, 50, 5049; (d) S. Jost, Y. Gimbert and A. E.
Greene, J. Org. Chem., 1997, 62, 6672; (e) P. Rozan, Y. H. Kuo
and F. Lambein, Phytochemistry, 2001, 58, 281; (f) L. B.
Snyder, Z. Meng, R. Mate, S. V. D. Andrea, A. Marinier, C. A.
Quesnelle, P. Gill, K. L. DenBleyker, J. C. F. Tomc, M. B.
Frosco, A. Martel, J. F. Barrett and J. J. Bronson, Bioorg. Med.
Chem. Lett., 2004, 14, 4735; (g) S. K. Laughlin, M. P. Clark, J.
F. Djung, A. Golebiowski, T. A. Brugel, M. Sabat, R. G.
Bookland, M. J. Laufersweiler, J. C. VanRens, J. F. Townes, B.
De, L. C. Hsieh, S. C. Xu, R. L. Walter, M. L. Mekel and M. J.
Janusz, Bioorg. Med. Chem. Lett., 2005, 15, 2399.
For recent reviews, see: (a) S. H. Cho, J. Y. Kim, J. Kwak and S.
Chang, Chem. Soc. Rev., 2011, 40, 5068; (b) G. Song, F. Wang
and X. Li, Chem. Soc. Rev., 2012, 41, 3651; (c) K. Shin, H. Kim
and S. Chang, Acc. Chem. Res., 2015, 48, 1040; (d) P. Ruiz-
Castillo and S. L. Buchwald, Chem. Rev., 2016, 116, 12564; (e)
D. A. Petrone, J. Ye and M. Lautens, Chem. Rev., 2016, 116,
8003; (f) R.-Y. Zhu, M. E. Farmer, Y.-Q. Chen and J.-Q. Yu,
Angew. Chem., Int. Ed., 2016, 55, 10578; (g) J. R. Hummel, J.
A. Boerth and J. A. Ellman, Chem. Rev., 2017, 117, 9163; (h)
S. Debbarma, M. R. Sk, B. Modak and M. S. Maji, J. Org.
Chem., 2019, 84, 6207; (i) A. Ford, H. Miel, A. Ring, C. N.
Slattery, A. R. Maguire and M. A. McKervey, Chem. Rev.,
2015, 115, 9981.
Cp*
Rh
Cl-
O
O
B
Scheme 4. A plausible mechanism.
Conclusions
In summary, we have developed rhodium-catalyzed cascade C-
H activation/intramolecular cyclization of 3-aryl-5-isoxazolones
with cyclic 2-diazo-1,3-diketones. Under the reaction
conditions, structurally diverse isoxazolo[2,3-f]phenanthridine
scaffolds could be produced in moderate-to-good yields. The
advantages of the current strategy include additive-free
conditions, good functional tolerance, and broad substrate
scope. Particularly noteworthy is that the by-products of N2
and H2O in the reaction make the process environmentally
benign. In addition, a large-scale synthesis and further
transformation are also presented to show the practicality and
potential of the current reaction.
9
Conflicts of interest
10 Selected literatures, see: (a) H. Wang, H. Xu, B. Li and B.
Wang, Org. Lett., 2018, 20, 5640 (b) Z. Yang, C. Pi, X. Cui and
Y. Wu, Org. Chem. Front., 2019, 6, 2897; (c) M. S. Sherikar
and K. R. Prabhu, Org. Lett., 2019, 21, 4525; (d) S. Huang, H.
Li, X. Sun, L. Xu, L. Wang and X. Cui, Org. Lett., 2019, 21,
5570; (e) C. Li and H. L. Qin, Org. Lett., 2019, 21, 4495; (f) Z.
Shen, C. Pi, X. Cui and Y. Wu, Chin. Chem. Lett., 2019, 30,
1374.
There are no conflicts to declare.
Acknowledgement
The work was partially supported by the National Natural
Science Foundation of China (No. 21772001), the Anhui
Provincial Natural Science Foundation (No. 1808085MB41),
and Cultivation Project for University Outstanding Talents of
Anhui Province (2019).
11 Selected literatures, see: (a) Y. Zhang, J. Zheng and S. Cui, J.
Org. Chem., 2014, 79, 6490; (b) X. Xu, Y. Yang, X. Zhang and
W. Yi, Org. Lett., 2018, 20, 566; (c) Y. Fukui, P. Liu, Q. Liu, Z.-
T. He, N.-Y. Wu, P. Tian and G.-Q. Lin, J. Am. Chem. Soc.,
2014, 136, 15607; (d) L. Song, X. Zhang, X. Tang, L. V.
Meervelt, J. Van der Eycken, J. N. Harvey and E. V. Van der
Eycken, Chem. Sci., 2020, 11, 11562; (e) B. Jiang, J. Jia, Y. Sun,
Y. Wang, J. Zeng, X. Bu, L. Shi, X. Sun and X. Yang, Chem.
Commun., 2020, 56, 13389; (f) S. Cai, C. Chen, P. Shao and C.
Xi, Org. Lett., 2014, 16, 3142; (g) X.-F. Cui and G.-S. Huang,
Org. Biomol. Chem., 2020, 18, 4014; (h) A.-Z. Cao, Y.-T. Xiao,
Y.-C. Wu, R.-J. Song, Y.-X. Xie and J.-H. Li, Org. Biomol. Chem.,
2020, 18, 2170; (i) C. Li, H.-B. Xu, J. Zhang, M. Liu and L.
Dong, Org. Biomol. Chem., 2020, 18, 1412.
Notes and references
1
(a) J. Liu, S. Narva, K. Zhou and W. Zhang, Mini-Rev. Med.
Chem., 2019, 19, 1571; (b) Z. Hosseinzadeh, A. Ramazani and
N. Razzaghi-Asl, Curr. Org. Chem., 2018, 22, 2256; (c) K. Du,
W. Yu, C. Shen, X. Chen and P. Zhang, Curr. Org. Synth., 2016,
13, 544; (d) M. Zhang, Q. Wang, Y. Peng, Z. Chen, C. Wan, J.
Chen, Y. Zhao, R. Zhang and A. Zhang, Chem. Commun.,
2019, 55, 13048; (e) M. R. Sk, S. S. Bera, S. Basuli, A. Metya
and M. S. Maji, Asian J. Org. Chem., 2020, 9, 1701.
12 (a) H. Huang, X. Ji, W. Wu and H. Jiang, Chem. Soc. Rev.,
4 | Org. Biomol. Chem., 2020, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins