A New Labdane Diterpene from the Flowers of Solidago canadensis

Abstract

Solidago canadensis L. is an Asteraceae widely distributed across North America, occurring in almost every state of the U.S.A. and throughout Canada. Numerous interesting secondary metabolites such as: flavonoids, phenolic acids and glucosides, polysaccharides, diterpenes, triterpenoid saponosides, tannins and essential oils 1) were reported for the genus Solidago. Previous phytochemical studies of S. canadensis have led to the isolation of flavonoids, 2,3) phenolic acids, 4) sesquiterpenes, 5) diterpenes 6,7) and saponins.7) The flowers of S. canadensis were used in traditional Amerindian medicine as an analgesic, 8) burns and ulcers treatment, 9) febrifuge, 10) gastrointestinal 11,12) and liver 11) aids. In spite of the widespread use of S. canadensis, few investigations were carried out on its bioactive secondary metabolites.Fractionation of the flower extracts of Solidago canadensis resulted in the isolation of a new diterpene, 9a,16x-dihydroxy-6-oxo-7,13-labdadien-15,16-olide (solicanolide, 1) and six known compounds identified as quercetin (2), 3-O-caffeoylquinic acid (neochlorogenic acid) (3), 5-O-caffeoylquinic acid (chlorogenic acid) (4), 4,5-di-O-caffeoylquinic acid (5), 3,5-di-O-caffeoylquinic acid (6) and 3,4-di-O-caffeoylquinic acid (7). To our knowledge, compound 7 was isolated for the first time in S. canadensis. This work describes the isolation of compounds 1-7 and the structure elucidation of a new compound identified as compound 1. The cytotoxicity of solicanolide (1) was also investigated in this paper. ExperimentalGeneral Experimental Procedures NMR spectra were recorded in methanol-d 4 on a Bruker Avance 400 spectrometer (5 mm QNP with Z-gradient probe) operating at 400.13 MHz ( 1 H) or 100.61 MHz ( 13 C). Chemical shifts were referenced relative to the corresponding residual solvent signals (d H/C 3.31/49.0 ppm, respectively). The accurate mass determination was carried out with an Applied Biosystems QSTAR XL Hybrid LC/MS/MS system. Optical rotation was obtained on a Jasco DIP-360 digital polarimeter. Analytical HPLC-DAD-MS analysis were performed on an Agilent 1100 series HPLC-DAD-MS system. A Zorbax ODS C18 column (5 mm, 150ϫ4.6 mm) maintained at 25°C was utilised. The flow rate was 1 ml/min. Agilent G1315B diode array detector was used for UV detection. The UV spectra were recorded from 190 to 400 nm. An Agilent mass selective detector (VL model) equipped with an atmospheric chemical ionisation source (APCI) was employed for MS detection. All mass spectra were acquired in the negative ion mode. The full scan mass spectrum was recorded over the range of m/z 100-1000. Temperature of the drying gas (N 2 ) was 350°C with a gas flow rate of 10 l/min and a nebulizing pressure of 40 psi. The ionisation voltage was 4000 V and the corona current was 15 mA. All HPLC separations were performed on a preparative Agilent 1100 series (Agilent Technologies Canada Inc.) with a ZORBAX ODS column C18 (2.1ϫ25 cm; 7 mm) at a flow rate of 16 ml/min. Compounds were detected by UV absorption at 254 nm. For all...

A Clinical Trial with Brazilian Arnica (Solidago chilensis Meyen) Glycolic Extract in the Treatment of Tendonitis of Flexor and Extensor Tendons of Wrist and Hand

“…At 363.18131 (C 20 H 27 O 6 ) and at 347.18640 (C 20 H 27 O 5 ) diterpenes with DBE of 7 can be solidagenone derivatives with oxidized furan ring. Bradette‐Hébert et al () isolated from Solidago canadensis the diterpene solicanolide with M = C 20 H 28 O 6 . Solicanolide‐type diterpenes with ethyl ether as side chains (M = C 24 H 40 O 7 and C 24 H 38 O 6 ) are also detected, because 10 hydrogens and one oxygen (CH 3 CH 2 O) were probably added to C 20 H 28 O 5 and C 20 H 28 O 6 , respectively.…”

In vivo anti-inflammatory activity of caffeoylquinic acid derivatives from Solidago virgaurea in rats

“…This is the first report of 3,4,5-tri-O-caffeoylquinic acid (3) in Solidago species. 3,5-Di-O-caffeoylquinic acid (1) was previously isolated from S. virgaurea (Thiem et al 2001;Choi et al 2004), while 3,4-di-O-caffeoylquinic acid (2) and 4,5-di-O-caffeoylquinic acid (4) were previously reported in other Solidago species (Bradette-Hebert et al 2008). …”

Evaluation of gastroprotective activity and acute toxicity ofSolidago chilensisMeyen (Asteraceae)

“…Other authors reported the presence of sesquiterpenes, labdane diterpenes, saponins, chlorogenic acid and caffeic acid in Solidago species (Bader et al, 1995;Apati et al, 2002;Bradette-Hébert et al, 2008;Steliopoulos et al, 2008).…”