1
Benzomalvin C (2). White crystals. H NMR (400 MHz, CDCl , δ, ppm, J/Hz): 8.25 (1H, dd, J = 8.0, 1.2, H-12),
3
7.96 (1H, dd, J = 8.0, 1.2, H-4), 7.93 (1H, br.d, J = 8.0, H-15), 7.84 (1H, m, H-14), 7.58 (1H, m, H-5), 7.55 (1H, m, H-13), 7.43
(1H, td, J = 8.0, 1.2, H-6), 7.18 (1H, m, H-24), 7.07 (2H, t, J = 7.5, H-23, 25), 6.89 (1H, br.d, J = 8.0, H-7), 6.62 (2H, br.d,
13
J = 7.5, H-22, 26), 3.89 (1H, s, H-20), 3.25 (3H, s, H-27). C NMR (100 MHz, CDCl , δ, ppm): 165.8 (C-2), 160.5 (C-10),
3
148.1 (C-18), 146.1 (C-16), 135.4 (C-14), 132.1 (C-8), 131.7 (C-3), 131.1 (C-6), 130.3 (C-21), 129.8 (C-4), 129.5 (C-24),
129.2 (C-5), 128.7 (C-7), 128.4 (C-23, 25), 128.4 (C-13), 128.3 (C-15), 127.7 (C-12), 126.0 (C-22, 26), 122.0 (C-11), 72.3 (C-19),
+
68.1 (C-20), 29.1 (C-27). (+)-ESI-MS m/z 396 [M + H] .
X-Ray Crystallographic Analysis of 2. White crystals of 2 were obtained from MeOH. The crystal data were recorded
°
at 293 K on an Agilent Gemini Ultra diffractometer with Cu Kα radiation (λ = 1.54718 A). The structure was solved by direct
methods (SHELXL-97) and refined using full-matrix least-squares difference Fourier techniques. All nonhydrogen atoms
were refined anisotropically, and all hydrogen atoms were placed in idealized positions and refined as riding atoms with the
relative isotropic parameters.
°
Crystal Data for 2. C
H
N O , M = 395.41, monoclinic, space group P2 with a = 11.2116 (5) A ,
24 17
3
3
r
1
°
°
° 3
3
–1
b = 23.4715 (8) A, c = 23.2885 (8) A, β = 91.595(4), V = 6126.0 (4) A , Z = 2, D = 1.286 g/cm , μ(Cu Kα) = 0.705 mm ,
x
3
and F(000) = 2472. Crystal dimensions: 0.08 × 0.07 × 0.07 mm . Independent reflections: 20129. The final R values were
1
0.1232, Flack parameter = 0.05(9), and wR2 = 0.3142 (I > 2σ (I)). Crystallographic data have been deposited in the Cambridge
Crystallographic Data Centre No. 1982703.
1
Benzomalvin E (3). White crystals. H NMR (400 MHz, DMSO-d , δ, ppm, J/Hz): 8.24 (1H, dd, J = 8.0, 1.5, H-12),
6
7.93 (1H, ddd, J = 8.0, 7.0, 1.5, H-4), 7.88 (1H, dd, J = 8.0, 1.5, H-6), 7.82 (1H, dd, J = 8.0, 1.5, H-15), 7.76 (1H, m, H-5), 7.73
(1H, m, H-7), 7.71 (1H, m, H-14), 7.64 (1H, ddd, J = 8.0, 7.0, 1.5, H-13), 7.33 (3H, overlapped, H-23–25), 7.10 (1H, dd, J = 8.0,
13
1.5, H-22, 26), 5.87 (1H, s, 20-OH), 4.56 (1H, d, J = 10.5, H-19), 3.84 (1H, d, J = 10.5, H-20), 2.57 (3H, s, H-27). C NMR
(100 MHz, DMSO-d , δ, ppm): 164.7 (C-2), 161.2 (C-10), 153.1 (C-18), 146.3 (C-16), 141.2 (C-21), 135.2 (C-14), 132.6 (C-8),
6
131.7 (C-3), 131.2 (C-6), 130.0 (C-4), 129.1 (C-5), 129.0 (C-24), 128.4 (CH-23, 25), 128.2 (C-7), 127.7 (C-13), 127.3 (C-12),
+
126.8 (C-15), 126.4 (C-22, 26), 121.0 (C-11), 74.2 (C-19), 70.2 (C-20), 37.4 (C-27). (+)-ESI-MS m/z 398 [M + H] .
ACKNOWLEDGMENT
This work was supported by the Program of National Natural Science Foundation of China (No. 31772457) and the
Taishan Scholars Program, China (No. tsqn20161010).
REFERENCES
1.
2.
3.
4.
5.
X. M. Hou, Y. Hai, Y. C. Gu, C. Y. Wang, and C. L. Shao, Curr. Med. Chem., 26, 1 (2019).
X. M. Hou, R. F. Xu, Y. C. Gu, C. Y. Wang, and C. L. Shao, Curr. Med. Chem., 22, 3707 (2015).
H. Sun, C. J. Barrow, D. M. Sedlock, A. M. Gillum, and R. Cooper, J. Antibiot., 47, 515 (1994).
L. Rahbek, J. Breinholt, J. C. Frisvad, and C. Christophersen, J. Org. Chem., 64, 1689 (1999).
J. F. Liu, M. Kaselj, Y. Isome, J. Chapnick, B. L. Zhang, G. Bi, D. Yohannes, L. B. Yu, and C. M. Baldino,
J. Org. Chem., 70, 10488 (2005).
6.
7.
C. M. Cui, X. M. Li, C. S. Li, H. F. Sun, S. S. Gao, and B. G. Wang, Helv. Chim. Acta, 92, 1366 (2009).
F. H. Song, B. Ren, K. Yu, C. X. Chen, H. Guo, N. Yang, H. Gao, X. T. Liu, M. Liu, Y. J. Tong, H. Q. Dai, H. Bai,
J. D. Wang, and L. X. Zhang, Mar. Drugs, 10, 1297 (2012).
8.
9.
10.
L. Liu, Y. Y. Zheng, C. L. Shao, and C. Y. Wang, Mar. Life Sci. Technol., 1, 60 (2019).
X. M. Hou, T. M. Liang, Z. Y. Guo, C. Y. Wang, and C. L. Shao, Chem. Commun., 55, 1104 (2019).
X. M. Hou, Y. Y. Li, Y. W. Shi, Y. W. Fang, R. Chao, Y. C. Gu, C. Y. Wang, and C. L. Shao, J. Org. Chem.,
84, 1228 (2019).
11.
12.
S. Toshiyuki, O. Tomohiro, E. Shoji, K. Akikazu, Y. Eiji, and O. Yoshio, Tetrahedron, 54, 7997 (1998).
J. P. Jang, J. H. Jang, N. K. Soung, H. M. Kim, S. J. Jeong, Y. Asami, K. S. Shin, M. R. Kim, H. Oh, B. Y. Kim,
and J. S. Ahn, J. Antibiot., 65, 215 (2012).
13.
Q. M. Feng, Y. Feng, T. Y. Zhang, H. F. Wang, M. Y. Zhang, Y. Y. Wu, G. Chen, Y. X. Zhang, and Y. H. Pei,
Nat. Prod. Res., 1478 (2019).
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