三七内生真菌Talaromyces Purpureogenus中2个Drimane倍半萜绝对构型的鉴定

doi:10.7503/cjcu20170006

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (6): 1046.doi: 10.7503/cjcu20170006

三七内生真菌Talaromyces Purpureogenus中2个Drimane倍半萜绝对构型的鉴定

张冰洋, 马洋洋, 郭华, 朱华结(), 李婉()

药物化学与分子诊断教育部重点实验室, 河北省药物质量分析控制重点实验室,河北大学药学院, 保定 071002

收稿日期:2017-01-04 出版日期:2017-06-10 发布日期:2017-04-11
作者简介:联系人简介: 李婉, 女, 博士, 讲师, 主要从事药物设计与合成研究. E-mail: liwanjingmin@163.com;朱华结, 男, 博士, 教授, 博士生导师, 主要从事手性药物化学研究. E-mail: zhuhuajie@hotmail.com
基金资助:
河北大学人才引进项目、保定市科技支撑项目(批准号: 16ZF117)和河北大学超算中心项目资助.

Absolute Configuration Determination of Two Drimane Sesquiterpenoids from the Endophytic Fungi Talaromyces Purpureogenus of Panax notoginseng^†

ZHANG Bingyang, MA Yangyang, GUO Hua, ZHU Huajie^*(), LI Wan^*()

Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of Ministry Education,Key Laboratory of Pharmaceutical Quality Control of Hebei Province, College of Pharmaceutical Sciences,Hebei University, Baoding 071002, China

Received:2017-01-04 Online:2017-06-10 Published:2017-04-11
Contact: ZHU Huajie,LI Wan E-mail:zhuhuajie@hotmail.com;liwanjingmin@163.com
Supported by:
Supported by the Talent Researcher Program of Hebei University, China, the Science and Technology Support Project of Baoding City, China(No.16ZF117) and the Project of the High-Performance Computing Center of Hebei University, China.

摘要/Abstract

摘要：

采用经典柱色谱法从三七内生真菌Talaromyces purpureogenus中分离得到2个化合物(1和2), 经核磁共振波谱和质谱确认其结构均为Drimane倍半萜. 通过量子化学计算比较电子圆二色谱(ECD)、旋光(OR)与实验值的方法鉴定了化合物1和2的绝对构型. 生物活性测试结果显示, 化合物1对大肠杆菌(E. coli)具有一定的抗菌活性(MIC=25 μmol/L).

关键词: 三七内生真菌, 电子圆二色谱, 绝对构型, 抗菌活性

Abstract:

Two drimane sesquiterpenoids(1, 2) were isolated from cultures of the fungus Talaromyces purpureogenus. The planar structures were well established by NMR and mass spectrometry, and the absolute configurations(AC) were determined by comparing experimental electronic circular dichroism(ECD) and optical rotation(OR) of compounds 1 and 2 with the calculated ECD and OR data using quantum methods. Compounds 1 and 2 were evaluated for antibacterial activities against four spices of pathogenic bacteria, and the results showed that compound 1 had weak antibacterial activities against Escherichia coli(MIC=25 μmol/L).

Key words: Talaromyces purpureogenus, Electroic circalar dichroism(ECD), Absolute configuration, Antibacterial activity

中图分类号:

O629.9

TrendMD:

张冰洋, 马洋洋, 郭华, 朱华结, 李婉. 三七内生真菌Talaromyces Purpureogenus中2个Drimane倍半萜绝对构型的鉴定. 高等学校化学学报, 2017, 38(6): 1046.

ZHANG Bingyang, MA Yangyang, GUO Hua, ZHU Huajie, LI Wan. Absolute Configuration Determination of Two Drimane Sesquiterpenoids from the Endophytic Fungi Talaromyces Purpureogenus of Panax notoginseng^†. Chem. J. Chinese Universities, 2017, 38(6): 1046.

图/表 4

参考文献 36

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Atom	Compound 1		Atom	Compound 2
Atom	¹H NMR (400 MHz, DMSO), δ		¹³C NMR (100 MHz, DMSO), δ	¹H NMR (600 MHz,CDCl₃), δ	¹³C NMR (150 MHz, CDCl₃), δ
1	3.67,(s, 1H)	69.3, CH	1	5.00,(brs, 1H)	76.2, CH
2	1.46,(m, 1H), 1.89,(m, 1H)	25.2, CH₂	2	1.94,(t, J=13.8 Hz, 1H) 1.77,(brs, 1H)	23.6, CH₂
3	1.13,(m, 1H) 1.71,(m, 1H)	34.3, CH₂	3	1.61,(dt, J=3.0, 13.8 Hz, 1H) 1.35,(td, J=3.0, 13.8 Hz, 1H)	34.9, CH₂
4		32.1, C	4		32.6, C
5	2.08,(dd, J=4.8, 10.0 Hz, 1H)	37.4, CH	5	2.51,(dd, J=6.0, 10.2 Hz, 1H)	37.9, CH
6	1.67,(m, 2H)	28.3, CH₂	6	2.57,(dt, J=6.0, 20.4 Hz, 1H) 2.24,(m, 1H)	25.6, CH₂
7	4.21,(brs, 1H)	58.4, CH	7	6.99,(t, J=3.0 Hz, 1H)	139.9, CH
8		125.0, C	8		130.5, C
Atom	Compound 1		Atom	Compound 2
Atom	¹H NMR (400 MHz, DMSO), δ		¹³C NMR (100 MHz, DMSO), δ	¹H NMR (600 MHz,CDCl₃), δ	¹³C NMR (150 MHz, CDCl₃), δ
9		173.2, C	9		78.0, C
10		42.1, C	10		41.1, C
11	4.91,(d, J=5.2Hz, 1H) 4.94,(d, J=5.2 Hz, 1H)	68.1, CH₂	11	4.39,(d, J=10.2 Hz, 1H) 4.25,(d, J=10.2 Hz, 1H)	74.1, CH₂
12		174.1, C	12		168.7, C
13	0.88,(s, 3H)	32.7, CH₃	13	1.03,(s, 3H)	33.0, CH₃
14	0.84,(s, 3H)	21.4, CH₃	14	1.02,(s, 3H)	21.7, CH₃
15	1.01,(s, 3H)	19.2, CH₃	15	0.91,(s, 3H)	18.6, CH₃
1'			1'		170.9, C
2'			2'	4.34,(t, J=6.6 Hz, 1H)	59.0, CH
3'			3'	2.20,(m, 1H)	30.0, CH
4'			4'	1.01,(d, J=6.6 Hz, 3H)	19.3, CH₃
5'			5'	0.98,(d, J=6.6 Hz, 3H)	18.0, CH₃
Ac			Ac		170.0, C
Ac CH₃			Ac CH₃	2.05,(s, 3H)	23.1, CH₃
NH			NH	6.12,(brd, J=6.6 Hz, 1H)

Atom	Compound 1		Atom	Compound 2
Atom	¹H NMR (400 MHz, DMSO), δ		¹³C NMR (100 MHz, DMSO), δ	¹H NMR (600 MHz,CDCl₃), δ	¹³C NMR (150 MHz, CDCl₃), δ
1	3.67,(s, 1H)	69.3, CH	1	5.00,(brs, 1H)	76.2, CH
2	1.46,(m, 1H), 1.89,(m, 1H)	25.2, CH₂	2	1.94,(t, J=13.8 Hz, 1H) 1.77,(brs, 1H)	23.6, CH₂
3	1.13,(m, 1H) 1.71,(m, 1H)	34.3, CH₂	3	1.61,(dt, J=3.0, 13.8 Hz, 1H) 1.35,(td, J=3.0, 13.8 Hz, 1H)	34.9, CH₂
4		32.1, C	4		32.6, C
5	2.08,(dd, J=4.8, 10.0 Hz, 1H)	37.4, CH	5	2.51,(dd, J=6.0, 10.2 Hz, 1H)	37.9, CH
6	1.67,(m, 2H)	28.3, CH₂	6	2.57,(dt, J=6.0, 20.4 Hz, 1H) 2.24,(m, 1H)	25.6, CH₂
7	4.21,(brs, 1H)	58.4, CH	7	6.99,(t, J=3.0 Hz, 1H)	139.9, CH
8		125.0, C	8		130.5, C
Atom	Compound 1		Atom	Compound 2
Atom	¹H NMR (400 MHz, DMSO), δ		¹³C NMR (100 MHz, DMSO), δ	¹H NMR (600 MHz,CDCl₃), δ	¹³C NMR (150 MHz, CDCl₃), δ
9		173.2, C	9		78.0, C
10		42.1, C	10		41.1, C
11	4.91,(d, J=5.2Hz, 1H) 4.94,(d, J=5.2 Hz, 1H)	68.1, CH₂	11	4.39,(d, J=10.2 Hz, 1H) 4.25,(d, J=10.2 Hz, 1H)	74.1, CH₂
12		174.1, C	12		168.7, C
13	0.88,(s, 3H)	32.7, CH₃	13	1.03,(s, 3H)	33.0, CH₃
14	0.84,(s, 3H)	21.4, CH₃	14	1.02,(s, 3H)	21.7, CH₃
15	1.01,(s, 3H)	19.2, CH₃	15	0.91,(s, 3H)	18.6, CH₃
1'			1'		170.9, C
2'			2'	4.34,(t, J=6.6 Hz, 1H)	59.0, CH
3'			3'	2.20,(m, 1H)	30.0, CH
4'			4'	1.01,(d, J=6.6 Hz, 3H)	19.3, CH₃
5'			5'	0.98,(d, J=6.6 Hz, 3H)	18.0, CH₃
Ac			Ac		170.0, C
Ac CH₃			Ac CH₃	2.05,(s, 3H)	23.1, CH₃
NH			NH	6.12,(brd, J=6.6 Hz, 1H)

三七内生真菌Talaromyces Purpureogenus中2个Drimane倍半萜绝对构型的鉴定

Absolute Configuration Determination of Two Drimane Sesquiterpenoids from the Endophytic Fungi Talaromyces Purpureogenus of Panax notoginseng^†

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