Three New C19-Diterpenoid Alkaloids from Aconitum brevicalcaratum

doi:10.6023/cjoc202211014

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (6): 2245-2251.DOI: 10.6023/cjoc202211014 Previous Articles Next Articles

短距乌头中三个新的C₁₉-二萜生物碱

邢凤^a^,^b, 曾浩^a, 李茜^a, 万丹^a, 丁欢欢^a, 谢江^c, 陈琳^a^,^*(), 周先礼^a^,^b^,^c^,^*()

a 西南交通大学生命科学与工程学院成都 610031
b 西南交通大学教育部材料先进技术重点实验室成都 610031
c 西南交通大学附属医院成都第三人民医院成都 610031

收稿日期:2022-11-10 修回日期:2022-12-21 发布日期:2023-01-11
基金资助:
国家自然科学基金(82073734); 四川省应用基础(2021YJ0222); 四川省中医药管理研究基金(2020HJZX002); 中央高校基本科研业务费专项(2682021CX085); 大学生创新创业培训计划(202210613076)

Three New C₁₉-Diterpenoid Alkaloids from Aconitum brevicalcaratum

Feng Xing^a^,^b, Hao Zeng^a, Qian Li^a, Dan Wan^a, Huanhuan Ding^a, Jiang Xie^c, Lin Chen^a,*(), Xianli Zhou^a^,^b^,^c,*()

a School of Life Science and Engineering, Southwest Jiaotong University, Chengdu 610031
b Key laboratory of Advanced Technologies of Materials, Ministry of Education, Southwest Jiaotong University, Chengdu 610031
c Affiliated Hospital of Southwest Jiaotong University ＆ The Third People Hospital of Chengdu, Chengdu 610031

Received:2022-11-10 Revised:2022-12-21 Published:2023-01-11
Contact: * E-mail: linch@swjtu.edu.cn; zhouxl@swjtu.edu.cn
Supported by:
National Natural Foundation of China(82073734); Science and Technology Support Programs of Sichuan Province(2021YJ0222); Research Foundation for Administration of Traditional Chinese Medicine of Sichuan Province(2020HJZX002); Fundamental Research Funds for Central Universities(2682021CX085); College Students' Innovative Entrepreneurial Training Plan Program(202210613076)

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Abstract

Three new C₁₉-diterpenoid alkaloids, brevicalcarines A~C (1~3), together with seven known compounds (4~10), were isolated from the roots of A. brevicalcaratum (Finet et Gagnep.) Diels. Their structures were determined by HR-ESI-MS (high resolution electrospray ionization mass spectroscopy), IR (Infrared absorption spectroscopy), 1D NMR (One-dimensional nuclear magnetic resonance), 2D NMR (Two-dimensional nuclear magnetic resonance) and X-ray crystallographic analysis. Brevicalcarine A (1) was a new diterpenoid alkaloid with vaginatunine A fragment at C-18, while brevicalcarine B (2) and brevicalcarine C (3) were new C₁₉-diterpenoid alkaloid with an acetoxy group at C-18. In addition, the anti-neuroinflammatory activity of these compounds against BV-2 cells was investigated, which showed that none of them had significant anti-neuroinflammatory activity.

Key words: ranunculaceae, Aconitum brevicalcaratum, diterpenoid alkaloid, anti-neuroinflammatory activity

Cite this article

Feng Xing, Hao Zeng, Qian Li, Dan Wan, Huanhuan Ding, Jiang Xie, Lin Chen, Xianli Zhou. Three New C₁₉-Diterpenoid Alkaloids from Aconitum brevicalcaratum[J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2245-2251.

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References 21

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No.	Compound 1			Compound 2			Compound 3
No.	δ_C^a	δ_H(J in Hz)^b		δ_C^c	δ_H(J in Hz)^d		δ_C^c	δ_H(J in Hz)^d
1	85.4 d	3.14~3.16 m		85.6 d	3.05~3.11 m		85.4 d	3.08~3.15 m
2	25.5 t	2.33~2.35 m, β		26.4 t	2.27~2.29 m, β		26.2 t	2.23~2.25 m, β
	—	2.02~2.07 m, α		—	1.94~1.98 m, α		—	1.93~1.96 m, α
3	32.9 t	1.86~1.87 m, β		32.6 t	1.69~1.77 m, β		32.0 t	1.73~1.79 m, β
	—	1.45~1.48 m, α		—	1.31~1.34 m, α		—	1.25~1.28 m, α
4	38.2 s	—		37.8 s	—		37.7 s	—
5	45.9 d	1.63~1.68 m		46.4 d	1.54~1.60 m		45.4 d	1.57~1.61 m
6	26.4 t	1.97~2.00 m, β		25.3 t	1.90~1.94 m, β		24.5 t	1.96~1.99 m, β
	—	1.83~1.85 m, α		—	2.25~2.27 m, α		—	1.33~1.38 m, α
7	45.9 d	2.08~2.12 m		45.9 d	2.06~2.10 m		41.1 d	2.33~2.37 m
8	74.1 s	—		74.1 s	—		77.5 s	—
9	45.5 d	1.82~1.84 m		45.5 d	1.80~1.86 m		42.9 d	2.26^e
10	37.0 d	2.35~2.38 m		37.0 d	2.34~2.37 m		39.4 d	2.26^e
11	49.1 s	—		48.9 s	—		49.4 s	—
12	29.6 t	2.31~2.33 m, β		29.6 t	2.31~2.34 m, β		29.6 t	2.20~2.23 m, β
	—	1.87~1.89 m, α		—	1.77~1.80 m, α		—	1.79~1.82 m, α
13	46.5 d	2.25~2.29 m		46.4 d	2.24~2.25 m		45.8 d	1.82~1.88 m
14	84.5 d	3.67 t (4.8)		84.5 d	3.67 t (4.8)		84.0 d	3.53 t (4.8)
15	41.8 t	2.28~2.30 m, α		41.8 t	2.29~2.31 m, α		36.2 t	2.11~2.19 m, α
	—	1.90~1.96 m, β		—	1.86~1.91 m, β		—	1.99~2.02 m, β
16	82.7 d	3.17~3.20 m		82.7 d	3.19~3.20 m		84.1 d	3.16~3.22 m
17	62.1 d	2.96 s		62.3 d	2.92 s		61.6 d	2.83 s
18	71.4 t	4.12 ABq (10.8), β		70.5 t	3.80 ABq (10.8), β		70.4 t	3.82 ABq (10.8), β
	—	4.01 ABq (10.8), α		—	3.75 ABq (10.8), α		—	3.78 ABq (10.8), α
19	52.9 t	2.63 ABq (10.8), α		52.8 t	2.50~2.55 m, α		53.2 t	2.51~2.56 m, α
	—	2.14 ABq (10.8), β		—	1.98~2.02 m, β		—	2.02~2.04 m, β
21	49.4 t	2.49~2.56 m, β		49.4 t	2.45~2.50 m, β		49.3 t	2.56~2.64 m, β
	—	2.38~2.45 m, α		—	2.36~2.42 m, α		—	2.45~2.50 m, α
22	13.7 q	1.08 t (7.2)		13.7 q	1.05 t (7.2)		13.4 q	1.09 t (7.2)
1-OCH₃	56.4 q	3.28 s		56.4 q	3.27 s		56.5 q	3.28 s
14-OCH₃	57.9 q	3.38 s		57.9 q	3.31 s		57.8 q	3.37 s
16-OCH₃	56.4 q	3.32 s		56.4 q	3.39 s		56.6 q	3.35 s
18-OCO	—	—		171.3 s	—		171.3 s	—
18-OAc	—	—		21.0 q	2.04 s		21.0 q	2.05 s
8-OEt	—	—		—	—		55.6 t	3.33~3.34 m, α
	—	—		—	—		—	3.31~3.33 m, β
	—	—		—	—		16.3 q	1.08 t (7.2)
1'	115.9 s	—		—	—		—	—
2'	141.5 s	—		—	—		—	—
3'	121.0 d	8.83 dd (1.2, 8.4)		—	—		—	—
4'	134.9 d	7.58~7.63 m		—	—		—	—
5'	123.3 d	7.14~7.18 m		—	—		—	—
6'	130.9 d	8.02 dd (1.6, 8.0)		—	—		—	—
7'	168.6 s	—		—	—		—	—
8'	167.8 s	—		—	—		—	—
1''	121.3 s	—		—	—		—	—
2''	140.0 s	—		—	—		—	—
3''	121.5 d	8.72 dd (1.2, 8.4)		—	—		—	—
4''	133.3 d	7.51~7.56 m		—	—		—	—
5''	123.7 d	7.22 td (1.2, 7.6, 7.6)		—	—		—	—
6''	127.4 d	7.86 dd (1.6, 8.0)		—	—		—	—
7''	175.9 s	—		—	—		—	—
9''	28.1 q	1.56 s		—	—		—	—
No.		Compound 1			Compound 2			Compound 3
No.		δ_C^a	δ_H(J in Hz)^b		δ_C^c	δ_H(J in Hz)^d		δ_C^c	δ_H(J in Hz)^d
10''		28.1 q	1.56 s		—	—		—	—
2'-NH		—	12.05 s		—	—		—	—
2''-NH		—	11.93 s		—	—		—	—

No.	Compound 1			Compound 2			Compound 3
No.	δ_C^a	δ_H(J in Hz)^b		δ_C^c	δ_H(J in Hz)^d		δ_C^c	δ_H(J in Hz)^d
1	85.4 d	3.14~3.16 m		85.6 d	3.05~3.11 m		85.4 d	3.08~3.15 m
2	25.5 t	2.33~2.35 m, β		26.4 t	2.27~2.29 m, β		26.2 t	2.23~2.25 m, β
	—	2.02~2.07 m, α		—	1.94~1.98 m, α		—	1.93~1.96 m, α
3	32.9 t	1.86~1.87 m, β		32.6 t	1.69~1.77 m, β		32.0 t	1.73~1.79 m, β
	—	1.45~1.48 m, α		—	1.31~1.34 m, α		—	1.25~1.28 m, α
4	38.2 s	—		37.8 s	—		37.7 s	—
5	45.9 d	1.63~1.68 m		46.4 d	1.54~1.60 m		45.4 d	1.57~1.61 m
6	26.4 t	1.97~2.00 m, β		25.3 t	1.90~1.94 m, β		24.5 t	1.96~1.99 m, β
	—	1.83~1.85 m, α		—	2.25~2.27 m, α		—	1.33~1.38 m, α
7	45.9 d	2.08~2.12 m		45.9 d	2.06~2.10 m		41.1 d	2.33~2.37 m
8	74.1 s	—		74.1 s	—		77.5 s	—
9	45.5 d	1.82~1.84 m		45.5 d	1.80~1.86 m		42.9 d	2.26^e
10	37.0 d	2.35~2.38 m		37.0 d	2.34~2.37 m		39.4 d	2.26^e
11	49.1 s	—		48.9 s	—		49.4 s	—
12	29.6 t	2.31~2.33 m, β		29.6 t	2.31~2.34 m, β		29.6 t	2.20~2.23 m, β
	—	1.87~1.89 m, α		—	1.77~1.80 m, α		—	1.79~1.82 m, α
13	46.5 d	2.25~2.29 m		46.4 d	2.24~2.25 m		45.8 d	1.82~1.88 m
14	84.5 d	3.67 t (4.8)		84.5 d	3.67 t (4.8)		84.0 d	3.53 t (4.8)
15	41.8 t	2.28~2.30 m, α		41.8 t	2.29~2.31 m, α		36.2 t	2.11~2.19 m, α
	—	1.90~1.96 m, β		—	1.86~1.91 m, β		—	1.99~2.02 m, β
16	82.7 d	3.17~3.20 m		82.7 d	3.19~3.20 m		84.1 d	3.16~3.22 m
17	62.1 d	2.96 s		62.3 d	2.92 s		61.6 d	2.83 s
18	71.4 t	4.12 ABq (10.8), β		70.5 t	3.80 ABq (10.8), β		70.4 t	3.82 ABq (10.8), β
	—	4.01 ABq (10.8), α		—	3.75 ABq (10.8), α		—	3.78 ABq (10.8), α
19	52.9 t	2.63 ABq (10.8), α		52.8 t	2.50~2.55 m, α		53.2 t	2.51~2.56 m, α
	—	2.14 ABq (10.8), β		—	1.98~2.02 m, β		—	2.02~2.04 m, β
21	49.4 t	2.49~2.56 m, β		49.4 t	2.45~2.50 m, β		49.3 t	2.56~2.64 m, β
	—	2.38~2.45 m, α		—	2.36~2.42 m, α		—	2.45~2.50 m, α
22	13.7 q	1.08 t (7.2)		13.7 q	1.05 t (7.2)		13.4 q	1.09 t (7.2)
1-OCH₃	56.4 q	3.28 s		56.4 q	3.27 s		56.5 q	3.28 s
14-OCH₃	57.9 q	3.38 s		57.9 q	3.31 s		57.8 q	3.37 s
16-OCH₃	56.4 q	3.32 s		56.4 q	3.39 s		56.6 q	3.35 s
18-OCO	—	—		171.3 s	—		171.3 s	—
18-OAc	—	—		21.0 q	2.04 s		21.0 q	2.05 s
8-OEt	—	—		—	—		55.6 t	3.33~3.34 m, α
	—	—		—	—		—	3.31~3.33 m, β
	—	—		—	—		16.3 q	1.08 t (7.2)
1'	115.9 s	—		—	—		—	—
2'	141.5 s	—		—	—		—	—
3'	121.0 d	8.83 dd (1.2, 8.4)		—	—		—	—
4'	134.9 d	7.58~7.63 m		—	—		—	—
5'	123.3 d	7.14~7.18 m		—	—		—	—
6'	130.9 d	8.02 dd (1.6, 8.0)		—	—		—	—
7'	168.6 s	—		—	—		—	—
8'	167.8 s	—		—	—		—	—
1''	121.3 s	—		—	—		—	—
2''	140.0 s	—		—	—		—	—
3''	121.5 d	8.72 dd (1.2, 8.4)		—	—		—	—
4''	133.3 d	7.51~7.56 m		—	—		—	—
5''	123.7 d	7.22 td (1.2, 7.6, 7.6)		—	—		—	—
6''	127.4 d	7.86 dd (1.6, 8.0)		—	—		—	—
7''	175.9 s	—		—	—		—	—
9''	28.1 q	1.56 s		—	—		—	—
No.		Compound 1			Compound 2			Compound 3
No.		δ_C^a	δ_H(J in Hz)^b		δ_C^c	δ_H(J in Hz)^d		δ_C^c	δ_H(J in Hz)^d
10''		28.1 q	1.56 s		—	—		—	—
2'-NH		—	12.05 s		—	—		—	—
2''-NH		—	11.93 s		—	—		—	—

Compound	50 µmol/L
Compound	Inhibition rate/%	Survival rate/%
1	5.72±1.95	104.40±1.54
2	5.18±0.69	103.00±1.15
3	3.47±3.40	103.40±1.16
4	3.20±1.39	107.00±1.85
5	1.20±1.06	105.90±0.72
6	3.52±0.56	102.30±1.15
7	12.69±0.60	98.61±2.81
8	4.44±1.54	106.30±4.62
9	1.20±1.06	103.10±2.90
10	16.26±0.70	96.90±4.33
Quercetin (20 µmol•L^–1)^a	61.94±0.78	99.38±3.96
Control	0.00±0.00	100.00±0.00

Compound	50 µmol/L
Compound	Inhibition rate/%	Survival rate/%
1	5.72±1.95	104.40±1.54
2	5.18±0.69	103.00±1.15
3	3.47±3.40	103.40±1.16
4	3.20±1.39	107.00±1.85
5	1.20±1.06	105.90±0.72
6	3.52±0.56	102.30±1.15
7	12.69±0.60	98.61±2.81
8	4.44±1.54	106.30±4.62
9	1.20±1.06	103.10±2.90
10	16.26±0.70	96.90±4.33
Quercetin (20 µmol•L^–1)^a	61.94±0.78	99.38±3.96
Control	0.00±0.00	100.00±0.00

短距乌头中三个新的C₁₉-二萜生物碱

Three New C₁₉-Diterpenoid Alkaloids from Aconitum brevicalcaratum

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[4]	Yin Tianpeng, Cai Le, Lei Gang, Dong Jianwei, Liu Yanxiong, Ding Zhongtao. Two New Diterpenoid Alkaloids from the Roots of Aconitum duclouxii Levl [J]. Chin. J. Org. Chem., 2013, 33(12): 2528-2532.
[5]	YAN Lu-Ping, CHEN Dong-Lin, WANG Feng-Peng. Structure Elucidation of Diterpenoid Alkaloids from Delphinium campylocentrum* [J]. Chin. J. Org. Chem., 2007, 27(08): 976-980.
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短距乌头中三个新的C19-二萜生物碱