To discriminate R and S flavanone glycoside using NMR, the mixture of R and S naringenin 7-O-glycoside was first isolated from Gleditsia sinensis. 1H and 13C NMR data of the mixture were recorded with 1H NMR, 13C NMR, 1H-1H COSY, 1H-13C HSQC and 1H-13C HMBC in DMSO-d6 solution. The two diastereomers were then separated with chiral chromatographic isolation, with their absolute configurations determined by circular dichroism. To avoid the disturbance of protons from glucose residues to dihydroflavonoid, 1H NMR spectra were acquired for pure R and S naringenin 7-O-glycoside and their mixture in CD3CN. The two diastereomers showed the largest proton chemical shift differences at the end group of glucose residue (H-1") with a chemical shift difference of 9.4 Hz. The OH-5 proton showed a chemical shift difference of 5.8 Hz. The chemical shift of the three protons on ring C were all influenced by configuration.
SUN Li-juan
,
HU Xiao-fang
,
CHENG Xun
,
LUO Li-ting
,
LIU Hong-bing
,
CHEN Lei
. NMR Characterization of Flavanone Naringenin 7-O-Glycoside Diastereomer[J]. Chinese Journal of Magnetic Resonance, 2017
, 34(4)
: 465
-473
.
DOI: 10.11938/cjmr20152418
[1]YAO L H.JIANG Y M,SHI J,et al.Flavonoids in food and their health benefits[J].Plant Food Hum Nutr,2004,59(3):113-122. [2]ANDERSON O M,MARKHAM K R.Flavanoids:chemistry,biochemistry and applications[M].Florida:CRC Press,2006. [3]CIRILLI R,FERRETTI R,DE SANTIS E,et al.High-performance liquid chromatography separation of enantiomers of flavanone and 2'-hydroxychalcone under reversed-phase conditions[J].J Chromatogr A,2008,1190(1,2):95-101. [4]PAN J Y,ZHANG S,YAN L S,et al.Separation of flavanone enantiomers and flavanone glucoside diastereomers from Balanophora involucrata Hook.f.by capillary electrophoresis and reversed-phase high-performance liquid chromatography on a C-18 column[J].J Chromatogr A,2008,1185(1):117-129. [5]ZUKOWSKI A J.Determination of diastereomerization barrier of some flavanones by high-performance liquid chromatography methods[J].J Chromatogr A,2006,1134(1,2):95-100. [6]CACCAMESE S,CARUSO C,PARRINELLO N.High-performance liquid chromatographic separation and chiroptical properties of the enantiomers of naringenin and other flavanones[J].J Chromatogr A,2005,1076(1,2):155-162. [7]SLADE D,FERREIRA D,MARAIS P.Circular dichroism,a powerful tool for the assessment of absolute configuration of flavonoids[J].Phytochemistry,2005,66(18):2177-2215. [8]XU M F,SHEN L Q,WANG K W.NMR characterization of two flavonyl glycosides isolated from Daphniphyllum angusticolium Hutch.[J].Chinese J Magn Reson,2010,27(2):259-265.许明峰,沈莲清,王奎武.虎皮楠中2个黄酮苷的波谱学研究[J].波谱学杂志,2010,27(2):259-265. [9]PENG S,HAN L F,LIU E W,et al.NMR characterization of two flavonyl glycosides isolated from Drynaria fortunei[J].Chinese J Magn Reson,2010,27(2):141-147.彭双,韩立峰,刘二伟,等.骨髓碎补中2个黄酮苷类化合物的NMR研究[J].波谱学杂志,2010,27(2):141-147. [10]SONG N,WANG R R,LI Z L,et al.Structure determination of flavonoid glycoside extracted from Capsella bursa-pastoris (L.) medic.by NMR spectroscopy[J].Chinese J Magn Reson,2009,26(1):89-92.宋宁,王荣荣,李占林,等.2D NMR对荠菜中的一个黄酮苷进行结构解析[J].波谱学杂志,2009,26(1):89-92. [11]HU Y Y,XIAO Y,ZHAO N,et al.Calculation of 13C chemical shifts of dihydroflavone using a model based on atomic electronegativity interaction vector[J].Chinese J Magn Reson,2005,22(4):383-389.胡银玉,肖燕,赵娜,等.二氢黄酮类化合物的核磁共振碳谱模拟研究[J].波谱学杂志,2005,22(4):383-389. [12]WILLIAM G,ROBERT L,BRUNO G,et al.C-2 stereochemistry of naringin and its relation to taste and biosynthesis in maturing grapefruit[J].Bioorg Chem,1975,4(3):259-269. [13]FEDERICA M,CORNELIS E,FRANK K,et al.Identification of natural epimeric flavanone glycosides by NMR spectroscopy[J].Food Chem,2009,116(2):575-579. [14]CRISTIANO F,THAIS P,DANIEL R,et al.Interconverting flavanone glucosides and other phenolic compounds in Lippia salviaefolia Cham ethanol extracts[J].Phytochemistry,2011,72(16):2052-2061. [15]WANG L,YU M M,CHI Y Q,et al.Chemical constituents of Euphorbia dracunculoides[J].China J Chin Mat Med,2014,39(20):3969-3973.王莉,喻明明,迟宇前,等.蒿状大戟化学成分研究[J].中国中药杂志,2014,39(20):3969-3973. [16]EHAB R,MOHAMMED H,HAZEM A,et al.Flavanone glycosides from Gleditsia caspia[J].J Nat Prods,2010,3:35-46. [17]HIROBUMI Y,HIROKI K,YASUHARU S.et al.Metabolism of administered (2 RS)-naringenin in flavonoid producing cultured cells of Sophora flavescens[J].Plant Biotech,2004,21(5):355-359.
