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Lignans from
Selaginella doederleinii and revision of structures of ten lignans- Acta Scientiarum Naturalium Universitatis Sunyatseni Vol. 60, Issue 3, Pages: 19-29(2021)
- 作者机构：
中山大学药学院，广东 广州 510006
- 作者简介：
- 基金信息：
DOI：10.13471/j.cnki.acta.snus.2020.03.21.2020C007
CLC： O625.4Published：25 May 2021，
Published Online：28 October 2020，
Received：21 March 2020，
Accepted：16 May 2020
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汤卓雅,潘月华,邹明锋等.深绿卷柏中木脂素成分及10个木脂素结构的修订[J].中山大学学报(自然科学版),2021,60(03):19-29.
TANG Zhuoya,PAN Yuehua,ZOU Mingfeng,et al.Lignans from Selaginella doederleinii and revision of structures of ten lignans[J].Acta Scientiarum Naturalium Universitatis Sunyatseni,2021,60(03):19-29.
汤卓雅,潘月华,邹明锋等.深绿卷柏中木脂素成分及10个木脂素结构的修订[J].中山大学学报(自然科学版),2021,60(03):19-29. DOI： 10.13471/j.cnki.acta.snus.2020.03.21.2020C007.
TANG Zhuoya,PAN Yuehua,ZOU Mingfeng,et al.Lignans from Selaginella doederleinii and revision of structures of ten lignans[J].Acta Scientiarum Naturalium Universitatis Sunyatseni,2021,60(03):19-29. DOI： 10.13471/j.cnki.acta.snus.2020.03.21.2020C007.
摘要
从传统中药深绿卷柏（
Selaginella doederleinii
）中分离得到5个已知的木脂素，并利用高分辨质谱及1D和2D NMR数据确定了其结构分别为3个8
4′-氧新木脂素类 [ (-)-赤式-(7′
E
)-4
9-二羟基-3
3′
5′-三甲氧基-8
4′-氧新木脂素-7′-烯-9′-醛 (
1
)、(-)-赤式-愈创木基甘油-
β
-
O
-4′-丁香树脂酚醚 (
2
) 和 (7′
E
)-3
5
3′
5′-四甲氧基-8
4′-氧新木脂素-7′-烯-4
9
9′-三醇 (
3
) ] ，1个苯骈呋喃类 [(+)-(7
R
8
S
)-5-甲氧二氢去氢二松柏醇 (
4
) ] 和1个双四氢呋喃类 [ 丁香脂素 (
5
) ] 。硫氧还蛋白氧化还原酶抑制活性评价显示3个化合物具有中等强度活性，其IC
50
值为10.1~20.2 μmol/L。化合物
1
~
4
是首次分离自该植物。另外，发现10个已知木脂素 [ 2
6
2′
6′-四甲氧基-4
4′-二(1-羟基-2
3-环氧丙基) 联苯 (
I
)、2
2′-二甲氧基-4
4′-二 (1-羟基-2
3-环氧丙基) 联苯 (
Ⅱ
)、2-羟基-3
2′
6′-三甲氧基-4′-(1-羟基-2
3-环氧丙基) -5-(3-羟基丙烯基) 联苯 (
Ⅲ
)、2-羟基-3
2′-二甲氧基-4′-(1-羟基-2
3-环氧丙基)-5-(3-羟基丙烯基) 联苯 (
Ⅳ
)、2
2′-二甲氧基-4-(3-羟基丙烯基)-4′-(1
2
3-三羟丙基) 二苯醚 (
Ⅴ
和
Ⅵ
)、(7′
R
8′
R
)-2
2'-二甲氧基-4-(3-羟丙烯基)-4′-(1
2
3-三羟丙基) 二苯醚 (
Ⅶ
)、野花椒乙素 (
Ⅷ
)、地黄新木甲素 (
Ⅸ
) 和地黄新木乙素 (
Ⅹ
) ] 的结构因解析不正确而误定为联苯新木脂素类和4
4′-氧新木脂素类。经过与模型化合物如一些报道的合成物及分离到的化合物（
1
~
5
）进行NMR数据对比分析后将化合物
Ⅰ
~
Ⅹ
的结构分别修订为(+)-丁香脂素(
5
)、(+)-松脂素(
6
)、(-)-simulanol(
7
)、(-)-去氢二松柏醇 (
8
)、(-)-苏式-愈创木基甘油-
β
-
O
-4′-松柏醇醚(
9
)、(+)-赤式-愈创木基甘油-
β
-
O
-4′-松柏醇醚 (
10a
)、(-)-赤式-愈创木基甘油-
β
-
O
-4′-松柏醇醚(
10b
)、(+)-苏式-愈创木基甘油-
β
-
O
-4′-丁香树脂酚醚 (
11
)、(-)-苏式-4-
O
-[1-羟甲基-2-羟基-2-(3-甲氧基-4-羟苯基) 乙基]阿魏酸甲酯(
12
)和(+)-赤式-4-
O
-[1-羟甲基-2-羟基-2-(3-甲氧基-4-羟苯基) 乙基]阿魏酸甲酯 (
13
) 。因此，尚无证据表明自然界中存在这10种木脂素，实际上其修正后的结构分别属于双四氢呋喃类
苯骈呋喃类及8
4′-氧新木脂素类等类型。
Abstract
Five known lignans including three 8，4′-oxyneolignans ［（-）-
erythro
-（7′
E
）-4，9-dihydroxy-3，3′，5′-trimethoxy-8，4′-oxyneolign-7′-en-9′-al （
1
）， （-）-
erythro
-guaiacylglycerol-
β
-
O
-4′-sinapyl ether （
2
）， and （7′
E
）-3，5，3′，5′-tetramethoxy-8，4′-oxyneolign-7′-ene-4，9，9′-triol （
3
）］， a benzofuran ［（+）-（7
R
，8
S
）-5-methoxydihydrodehydrodiconiferyl alcohol （
4
）］， and one furofuran ［syringaresinol （
5
）］ were isolated from the traditional Chinese medicine
Selaginella doederleinii
. Their structures were elucidated by HRMS and 1D and 2D NMR data. The inhibitory activities of
1
-
5
against thioredoxin reductase （TrxR） were evaluated， and three compounds showed moderate activities with IC
50
values ranging from 10.1 to 20.2 μmol/L. Compounds
1
-
4
were isolated from
S. doederleinii
for the first time. In addition， it was found that the structures of ten known lignans ［2，6，2′，6′-tetramethoxy-4，4′-bis（2，3-epoxy-1-hydroxypropyl）biphenyl （
Ⅰ
）， griffilignan A （
Ⅱ
）， 2-hydroxy-3，2′，6′-trimethoxy-4′-（2，3-epoxy-1-hydroxypropyl）-5-（3-hydroxy-l-propenyl）biphenyl （
Ⅲ
）， 2-hydroxy-3，2′-dimethoxy-4′-（2，3-epoxy-1-hydroxypropyl）-5-（3-hydroxy-1-propenyl）biphenyl （
Ⅳ
）， 2，2′-dimethoxy-4-（3-hydroxy-l-propenyl）-4′-（1，2，3-trihydroxypropyl）diphenyl ethers （
Ⅴ
and
Ⅵ
）， （7΄
R
，8΄
R
）-2，2′-dimethoxy-4-（3-hydroxyl-propenyl）-4′-（1，2，3-trihydroxypropyl）biphenyl ether （
Ⅶ
）， utiline B （
Ⅷ
）， and rhemaneolignans A and B （Ⅸ and
Ⅹ
）］ were erroneously identified as the types of biphenylneolignans and 4，4′-oxyneolignans due to incorrect elucidation. By comparison of their NMR data with those of model compounds such as some reported synthetic products and the isolates （
1
-
5
）， the structures of
Ⅰ
-
Ⅹ
were revised as （+）-syringaresinol （
5
）， （+）-pinoresinol （
6
）， （-）-simulanol （
7
）， （-）-dehydrodiconiferyl alcohol （
8
）， （-）-
threo
-guaiacylglycerol-
β
-
O
-4′-coniferyl ether （
9
）， （+）-
erythro
-guaiacylglycerol-
β
-
O
-4′-coniferyl ether （
10a
）， （-）-
erythro
-guaiacylglycerol-
β
-
O
-4′-coniferyl ether （
10b
）， （+）-
threo
-guaiacylglycerol-
β
-
O
-4′-sinapyl ether （
11
）， （-）-
threo
-methyl 4-
O
-［2-hydroxy-2-（4-hydroxy-3-methoxyphenyl）-1-（hydroxymethyl）ethyl］ferulate （
12
）， and （+）-
erythro
-methyl 4-
O
-［2-hydroxy-2-（4-hydroxy-3-methoxyphenyl）-1-（hydroxymethyl）ethyl］ferulate （
13
）， respectively. So， it noteworthy that there is no evidence for the existence of the ten lignans in nature， and their revised structures are actually represented as the types of furofurans， benzofurans， and 8，4′-oxyneolignans， respectively.
关键词
卷柏科（Selaginellaceae）深绿卷柏（Selaginella doederleinii）木脂素联苯新木脂素结构修订
Keywords
SelaginellaceaeSelaginella doederleiniilignanbiphenylneolignanstructural revision
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