天然產(chǎn)物中木栓烷型三萜核磁共振波譜特征

劉向前，李小軍,，金倫喆，陸昌洙（

1.湖南中醫(yī)藥大學(xué)藥學(xué)院，湖南長沙410208；2.圓光大學(xué)藥學(xué)院，韓國益山570-749；3.慶熙大學(xué)藥學(xué)院，韓國首爾130-701）

天然產(chǎn)物中木栓烷型三萜核磁共振波譜特征

劉向前1，李小軍1,2，金倫喆2，陸昌洙3（

1.湖南中醫(yī)藥大學(xué)藥學(xué)院，湖南長沙410208；2.圓光大學(xué)藥學(xué)院，韓國益山570-749；3.慶熙大學(xué)藥學(xué)院，韓國首爾130-701）

對天然產(chǎn)物中發(fā)現(xiàn)的木栓烷型三萜化合物的13C-NMR、1H-NMR譜學(xué)特征進(jìn)行綜述，以期減少天然產(chǎn)物特別是木栓烷型三萜結(jié)構(gòu)鑒定工作的盲目性和重復(fù)性，為進(jìn)一步研究分析木栓烷型三萜提供經(jīng)驗借鑒。

木栓烷型三萜；核磁波譜特征；13C-NMR；1H-NMR

本文引用：劉向前，李小軍，金倫喆，陸昌洙.天然產(chǎn)物中木栓烷型三萜核磁共振波譜特征[J].湖南中醫(yī)藥大學(xué)學(xué)報，2017，37（1）：87-105.

木栓烷型（friedelane type）三萜及其皂苷主要分布于衛(wèi)矛科（Celastraceae）、翅子藤科（Hippocrateaceae）、大戟科（Euphorbiaceae）、大風(fēng)子科（Flacourtiaceae）和藤黃科（Guttiferae/Clusiaceae）等植物中，衛(wèi)矛科（Celastraceae）和翅子藤科（Hippocrateaceae）中尤為常見?，F(xiàn)代藥理學(xué)研究表明，該類化合物具有抗腫瘤、抗炎、抗-HIV、抗菌、抗白血病和抗氧化等藥理活性作用［1-6］。早在20世紀(jì)70年代，藥物化學(xué)等領(lǐng)域的專家學(xué)者就對其進(jìn)行了熱門研究。近年來，越來越多結(jié)構(gòu)復(fù)雜、新穎的木栓烷型三萜被發(fā)現(xiàn)，因其具有良好的藥理活性而一直成為天然產(chǎn)物研究的熱點(diǎn)。

與其它天然產(chǎn)物研究一樣，木栓烷型三萜及其苷類化合物分離純化得到單體化合物后，更為重要的一步是其結(jié)構(gòu)和構(gòu)型的鑒定（結(jié)構(gòu)表征）。常用的波譜學(xué)鑒定方法主要有UV、IR、NMR、MS、X-Ray及CD等，其中一維和二維NMR在三萜的解析中起著至關(guān)重要的作用。通過FAB-MS、ESI-MS、HRMS和MSMS等質(zhì)譜技術(shù)可準(zhǔn)確測定木栓烷型三萜的分子量及相應(yīng)的結(jié)構(gòu)信息，一維和二維NMR綜合分析可快速確定三萜苷元、糖和苷元的連接位置、糖鏈結(jié)構(gòu)等信息，再綜合UV、IR、CD等鑒定手段和該物質(zhì)的理化性質(zhì)，以及必要的文獻(xiàn)查閱，可準(zhǔn)確地推測出其平面和立體結(jié)構(gòu)。

本文對1980-2015年已報道的246個木栓烷型三萜的13C-NMR和1H-NMR數(shù)據(jù)進(jìn)行歸納總結(jié)，以期有助于相關(guān)研究者進(jìn)行這類化合物的結(jié)構(gòu)鑒定，為進(jìn)一步分析研究木栓烷型三萜提供經(jīng)驗借鑒。

1 木栓烷型三萜的結(jié)構(gòu)類型

天然產(chǎn)物中的木栓烷型三萜根據(jù)其結(jié)構(gòu)特征主要分為5類：木栓烷型三萜（Intact friedelanes,TypeⅠ）、降碳類木栓烷型三萜（Norfriedelanes,TypeⅡ）、開環(huán)型木栓烷型三萜（Secofriedelanes,TypeⅢ）、環(huán)氧型木栓烷型三萜（Epoxyfriedelanes,TypeⅣ）和二聚體類木栓烷型三萜（Dimers,TypeⅤ）。從生物合成途徑來看，木栓烷型三萜及其衍生物由角鯊烯-2,3-環(huán)氧化物的環(huán)化而得，在木栓烷型三萜的基本母核的結(jié)構(gòu)基礎(chǔ)上再進(jìn)行碳環(huán)骨架的重排、轉(zhuǎn)化、氧化和聚合，得降碳類、開環(huán)型、環(huán)氧型和二聚體類木栓烷型三萜及其衍生物。它們的基本結(jié)構(gòu)類型和天然來源分別見圖1和表1。

圖1 木栓烷三萜I-V類型的代表性化合物

表1 木栓烷型三萜的天然來源

續(xù)表1

續(xù)表1

續(xù)表1

2 木栓烷型三萜的NMR特征

2.1 木栓烷型三萜的13C-NMR特征

木栓烷型三萜苷元中除了與氧相連的碳外，其余碳一般在δ60以下。在13C-NMR中，角甲基一般出現(xiàn)在δ6.2～35.5，其中23-CH3一般在6.2～13.5左右；23位為甲基時，24甲基的δ值為13.7～23.5；25-28位CH3的δ值一般出現(xiàn)在18～32；29-30位甲基δ值一般為31～35。無氧取代時，-CH2-的δ值一般分布于δ18-42左右，-CH-在δ37-60，而季碳的δ值則一般在δ33-57。木栓烷型三萜苷元和糖上與氧相連的碳δ值在60～90之間，具體而言，OH碳位δ61～82左右，乙酰基取代比相應(yīng)的OH取代向低場位移2～3左右。當(dāng)有單OH或多OH取代時，會因為取代基效應(yīng)而引起α-C向低場位移34～50，β-C向低場位移2～10左右，γ-C效應(yīng)與前面兩種效應(yīng)相反，向高場位移0～9。烯碳為δ109～160左右，羰基碳δ170～220，一般羰基碳在δ180左右，而形成酯鍵則稍向高場位移，醛基碳則一般在δ195～210左右。以下綜述了具有典型代表性的五類木栓烷型三萜的13C-NMR數(shù)據(jù)。

2.1.1 基本結(jié)構(gòu)木栓烷型三萜的13C-NMR特征

正常結(jié)構(gòu)的木栓烷型三萜的13C-NMR特征一般與上述相似，在角甲基無氧取代的情況下一般會出現(xiàn)8個角甲基信號，最具特征的是23-CH3一般在δ6.2～13.5左右，當(dāng)23-CH3為β型時，δ值一般在10以下；當(dāng)23-CH3為α型時，由于空間效應(yīng)的影響，其與24-CH3中的H的斥力作用減弱導(dǎo)致直接相連C的電子云密度減弱，從而減小了屏蔽效應(yīng)，化學(xué)位移移向低場，一般出現(xiàn)在δ13.5附近。當(dāng)相應(yīng)位置出現(xiàn)氧代時由于氧的吸電子效應(yīng)會使相應(yīng)的C的δ值升高。見表2。

2.1.2 降碳木栓烷型三萜的13C-NMR特征

降碳木栓烷型三萜一般降碳的位置出現(xiàn)在取代甲基部位：如23-nor（N47和N48）、24-nor（N8和N29-N33）、29-nor（N8）、30-nor（N49）等。此類三萜13CNMR最大特征就是甲基信號的相應(yīng)減少。見表3。

2.1.3 開環(huán)木栓烷型三萜的13C-NMR特征

該種類型的木栓烷型三萜最典型的結(jié)構(gòu)特征是母環(huán)中A環(huán)的開環(huán)，且最常見的開環(huán)位置一般為3,4-seco（如S2-S5、S10-S20）或2,3-seco（如S1、S6-S9）。在開環(huán)部位一般都有-O-原子的介入，使得相應(yīng)開環(huán)部位的化學(xué)位移向低場移動。另外，在開環(huán)的同時也常常伴隨著降碳現(xiàn)象的出現(xiàn)（S9、S16）。見表4。

2.1.4 環(huán)氧木栓烷型三萜的13C-NMR特征

該類型的三萜在結(jié)構(gòu)上保留了木栓烷母環(huán)的完整性，其結(jié)構(gòu)特點(diǎn)是在母環(huán)外接有環(huán)外的環(huán)氧橋，這使得環(huán)氧橋上與-O-原子相連的-C-原子化學(xué)位移向低場移動。見表5。

2.1.5 二聚體類木栓烷型三萜的13C-NMR特征

該類三萜的結(jié)構(gòu)特征是由2分子的木栓烷母環(huán)聚合而成，一般為一邊含有1個醌環(huán)（quinoid），具有典型的醌類化合物碳信號；另一邊帶有一個芳香環(huán)（aromatic），具有芳香化合物碳信號。通常各相應(yīng)位置的碳信號為成對出現(xiàn)的。見表6。

表2 正常結(jié)構(gòu)木栓烷型三萜的13C-NMR數(shù)據(jù)

續(xù)表2

C I68 I69 I70 I71 I72 I73 I74 I75 I76 I77 I78 1 2 3 4 5 6 7 8 9 1 0 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 22.3 41.7 212.8 58.8 41.3 49.0 68.4 52.9 37.2 60.0 37.6 30.5 40.4 39.1 32.4 35.8 30.5 41.6 29.6 33.1 27.9 39.4 6.9 16.1 19.0 21.8 18.3 32.1 74.5 26.0 74.0 30.1 213.2 53.3 42.7 41.2 18.2 53.0 36.9 52.4 35.9 30.5 39.8 38.4 32.1 35.4 30.0 42.7 28.9 33.4 28.2 28.1 6.9 14.3 17.9 20.0 18.7 32.2 28.9 72.0 74.0 29.7 213.2 53.3 42.7 41.2 18.1 53.1 36.9 52.4 32.7 29.5 39.7 38.0 30.2 35.3 30.0 42.4 31.3 40.2 28.2 38.2 6.8 14.3 17.5 20.9 17.7 32.0 31.8 183.1 27.6 41.2 213.0 57.9 41.7 40.7 17.8 51.5 37.4 59.0 34.8 30.4 37.5 38.4 32.6 29.3 42.4 38.5 34.1 32.8 31.0 22.0 6.6 14.3 17.0 19.0 16.1 177.0 26.7 79.7 19.3 36.3 71.9 52.9 37.4 40.9 17.4 52.6 37.0 59.6 35.6 30.9 37.8 38.6 32.3 29.2 44.5 37.6 34.5 28.2 35.1 32.2 9.6 14.3 17.4 20.3 18.3 183.7 29.5 34.2 22.3 41.1 212.1 58.0 42.1 40.7 18.3 53.2 43.8 58.9 51.3 213.1 54.1 42.4 32.1 27.2 47.2 30.3 35.8 28.7 32.8 34.0 6.9 14.5 17.6 20.1 19.0 209.5 34.0 29.1 25.0 41.6 213.3 58.1 43.1 42.2 17.9 52.8 44.1 60.1 76.9 42.0 41.1 38.2 32.4 35.9 30.0 42.5 35.4 28.1 32.7 39.2 6.9 14.8 12.9 20.1 19.5 32.0 31.7 35.0 22.3 41.1 212.0 58.1 42.2 40.9 18.6 52.2 44.4 59.3 51.2 214.3 55.6 44.0 30.0 29.3 34.5 33.1 33.7 28.3 36.1 31.0 6.9 14.6 18.4 18.1 19.7 68.5 33.3 33.6 22.3 41.3 212.8 58.2 41.9 41.1 18.2 52.1 38.4 59.4 47.2 73.0 44.8 40.5 37.5 32.1 36.0 40.3 31.7 28.3 33.4 29.3 6.8 14.6 19.5 19.2 12.2 67.8 34.0 32.9 22.17 41.34 212.20 57.91 41.96 40.82 18.54 52.32 37.51 58.99 35.24 28.95 38.96 40.59 50.17 218.38 45.68 43.24 30.14 32.68 27.04 31.14 6.87 14.56 17.25 20.27 15.93 27.44 74.06 25.84 22.22 41.43 212.78 58.04 42.14 41.11 18.41 53.32 37.42 59.31 35.61 30.74 40.06 39.11 44.28 74.40 36.45 44.09 30.36 33.14 27.51 36.45 6.88 14.60 18.06 20.08 21.43 25.44 74.45 25.71

表3 降碳木栓烷型三萜的13C-NMR數(shù)據(jù)

表4 開環(huán)木栓烷型三萜的13C-NMR數(shù)據(jù)

表5 環(huán)氧木栓烷型三萜的13C-NMR數(shù)據(jù)

表6 二聚體類木栓烷型三萜的13C-NMR數(shù)據(jù)

續(xù)表6

2.2 木栓烷型三萜的1H-NMR特征

在木栓烷型三萜氫譜中，主要包括甲基（-CH3）信號、亞甲基（-CH2-）信號、次甲基（-CH-）信號、雙鍵質(zhì)子（CH=CH）信號、以及常見的羥基（-OH）氫信號和羧基（-COOH）醛基（-CHO）等官能團(tuán)的活潑氫信號。

在木栓烷型三萜中，-CH3的氫化學(xué)位移在δ0.6-1.9之間，23-H一般以二重峰(d峰)出現(xiàn)，一般在δ1.0左右；非取代基直接連接的-CH2-一般在δ0.75-2.6之間,同一碳上的兩個氫因空間位置不同，位移相差δ0-0.9左右；非取代基直接相連的-CH-氫信號一般在δ0.67-2.75左右，4-H因與23-H相互偶合，一般以四重峰(q峰)出現(xiàn)。10和18-H則列分為2個二重峰(dd峰)。有OH等取代時，同碳H的δ值明顯向低場移動。表7～11綜述了具代表性的五類木栓烷型三萜的1H-NMR數(shù)據(jù)特征。

表7 正常結(jié)構(gòu)木栓烷型三萜的1H-NMR數(shù)據(jù)(mult,J in Hz)

續(xù)表7

表8 降碳木栓烷型三萜的1H-NMR數(shù)據(jù)(mult,J in Hz)

表9 開環(huán)木栓烷型三萜的1H-NMR數(shù)據(jù)(mult,J in Hz)

續(xù)表9

表10 環(huán)氧木栓烷型三萜的1H-NMR數(shù)據(jù)(mult,J in Hz)

表11 二聚體類木栓烷型三萜的1H-NMR數(shù)據(jù)(mult,J in Hz)

3 結(jié)論

木栓烷型三萜是五環(huán)三萜中具有潛在藥用價值的一類，其中一些化合物表現(xiàn)出了良好的生物活性，例如雷公藤紅素（celastrol,N36）、衛(wèi)矛酮（tingenone, N37）、扁塑藤素（pristimerin,N44）、violaic A（S10）、violaic B（S11）、violalide（S12）等，尤其是最近發(fā)現(xiàn)的結(jié)構(gòu)獨(dú)特且生物活性好的醌甲基化物降碳類、開環(huán)類、環(huán)氧類木栓烷型三萜，引起了許多相關(guān)研究者的極大關(guān)注。本文主要總結(jié)了近幾十年來天然來源的木栓烷型三萜的結(jié)構(gòu)特征，對這些化合物的NMR數(shù)據(jù)特征進(jìn)行了分類歸納，以期對木栓烷型三萜化合物的結(jié)構(gòu)解析研究提供一定的參考。

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（本文編輯 蘇維）

NMR Spectral Characteristics of Natural Friedelanes:A Review

LIU Xiangqian1,LI Xiaojun1,2,KIM Youn-chul2,YOOK Chang-soo3
(1.School of Pharmacy,Hunan University of Chinese Medicine,Changsha,Hunan 410208,China;
2.School of Pharmacy,Wonkwang University,Iksan 570-749,Korea;
3.School of Pharmacy,KyungHee University,Seoul 130-701,Korea)

The friedelane-type triterpenoids from natural products were studied in this paper including their chemical structures and spectral characteristics of13C-NMR,1H-NMR,so as to provide reference for reducing the blindness and repeatability of structure identification,and contribute to reducing some difficulties in the structure identification of friedelanetype triterpenoids,and provide theoretical basis for further research and analysis of friedelane-type triterpenoids.

friedelane-type triterpenoids;NMR spectral characteristics;13C-NMR;1H-NMR

R284.1

A

2016-04-12

湖南省中醫(yī)藥科研計劃項目(2013136)；湖南中醫(yī)藥大學(xué)藥物分析學(xué)“十二五”校級重點(diǎn)學(xué)科建設(shè)項目；湖南省中藥學(xué)重點(diǎn)學(xué)科建設(shè)項目。

劉向前，男，博士，教授，研究方向：天然產(chǎn)物活性成分研究，生藥活性成分與質(zhì)量評價研究，中藥化學(xué)與分析；E-mail: lxq0001cn@163.com。