Triterpene saponins from Billia rosea Luis De Freitas a, b , Doris Jimenez b , Sherley Pimentel b , Anne-Claire Mitaine-Offer a , Laurent Pouys  egu c , St  ephane Quideau c , Thomas Paululat d , Freddy Gonzalez-Mujica e , Luis B. Rojas f , María Rodríguez b , Marie-Aleth Lacaille-Dubois a, * a Laboratoire de Pharmacognosie, PEPITE EA 4267, UFR des Sciences de Sant e, Universit e de Bourgogne Franche-Comt e, 7, Bd. Jeanne d'Arc, BP 87900, F-21079 Dijon Cedex, France b Laboratorio de Productos Naturales, Escuela de Química, Facultad de Ciencias, Universidad Central de Venezuela, Caracas 47102, Venezuela c Institut des Sciences Mol eculaires, CNRSeUMR 5255 et Institut Europ een de Chimie et Biologie, Universit e de Bordeaux, 2 Rue Robert Escarpit, 33607 Pessac Cedex, France d Universit€ at Siegen, OC-II, Naturwissenschaftlich-Technische Fakult€ at, Adolf-Reichwein-Str. 2, D-57076 Siegen, Germany e Secci on de Bioquímica M edica, Instituto de Medicina Experimental, Facultad de Medicina, Universidad Central de Venezuela, Caracas 50587, Venezuela f Laboratorio de Productos Naturales, Departamento de Quimica, Facultad de Ciencias, Universidad de los Andes, M erida 5101, Venezuela article info Article history: Received 16 December 2016 Received in revised form 25 April 2017 Accepted 26 April 2017 Keywords: Billia rosea Sapindaceae Triterpene saponins Glucose-6-phosphatase Intestinal glucose absorption abstract Five previously undescribed triterpene saponins, billiosides A-E, and a known analogue, were isolated from the seeds of Billia rosea (Planch. & Linden) C. Ulloa & P. Jørg. Their structures were elucidated on the basis of extensive 1D and 2D NMR experiments ( 1 H, 13 C, DEPT, COSY, TOCSY, NOESY, ROESY, HSQC, and HMBC) and mass spectrometry as (3b,21b,22a)-3-[(2-O-b-D-glucopyranosyl-O-[a-L-arabinopyranosyl- (1 / 4)]-b-D-glucopyranosyl)oxy]-21-[((2E,6S)-2,6-dimethyl-6-hydroxyocta-2,7-dienoyl)oxy]-22-(ace- tyloxy)-24-hydroxyolean-12-en-28-oic acid, (3b,21b,22a)-3-[(2-O-b-D-galactopyranosyl-b-D-glucopyr- anosyl)oxy]-21,22-dihydroxyolean-12-en-28-yl O-a-L-arabinopyranosyl-(1 / 4)-b-D-glucopyranoside, (3b,21b,22a)-3-[(2-O-b-D-galactopyranosyl-O-[a-L-arabinopyranosyl-(1 / 4)]-b-D-xylopyranosyl)oxy]- 21,22-dihydroxyolean-12-en-28-yl O-b-D-glucopyranoside, (3b,21b,22a)-3-[(2-O-b-D-galactopyranosyl- O-[a-L-arabinopyranosyl-(1 / 4)]-b-D-glucopyranosyl)oxy]-21,22-dihydroxyolean-12-en-28-yl O-b-D- glucopyranoside, (3b,21b,22a)-3-[(2-O-b-D-galactopyranosyl-O-[a-L-arabinopyranosyl-(1 / 4)]-b-D- glucopyranosyl)oxy]-21,22-dihydroxyolean-12-en-28-yl O-b-D-glucopyranosyl-(1 / 6)-b-D-glucopyr- anoside, and dipteroside A. Billiosides B and C exhibited moderate effects when tested as hepatic glucose-6-phosphatase inhibitors and as glucose intestinal absorption inhibitors, using in situ rat in- testinal segments. © 2017 Elsevier Ltd. All rights reserved. 1. Introduction Billia is a genus of two species, Billia hippocastanum Peyr. and Billia rosea (Planch. & Linden) C. Ulloa & P. Jorg. (Sapindaceae) distributed in Central America and South America, respectively (Harris et al., 2016; Forest et al., 2001; Moreno, 1985). Billia rosea seeds have been used in infusions for their analgesic and antidia- betic properties (Giraldo et al., 2009). This plant together with the genera Aesculus and Handeliodendron belongs to the clade Hippo- castaneae, in the Sapindaceae family (Harris et al., 2016). The genus Handeliodendron is represented by one species, Handeliodendron bodinieri, localized in southwest China (Harris et al., 2016; Cao et al., 2008). The genus Aesculus is represented by 12 species distributed throughout the northern hemisphere (East Asia, North America and Europe) (Harris et al., 2016). Numerous phytochemical studies on Aesculus reported the isolation of oleanane-type saponins (Lanzotti et al., 2012; Yuan et al., 2012, 2013, 2015). However, there are no previous phytochemical studies on Billia rosea and Handelioden- dron. This paper describes the isolation and structure elucidation of five previously undescribed triterpene saponins named billiosides A-E (1e5; Fig. 1) together with a known analogue from the MeOH extract of the seeds of B. rosea. Hepatic glucose-6-phosphatase in- hibition and in situ rat intestinal absorption inhibition of glucose of the compounds 2 and 3 were also evaluated. * Corresponding author. E-mail address: m-a.lacaille-dubois@u-bourgogne.fr (M.-A. Lacaille-Dubois). Contents lists available at ScienceDirect Phytochemistry journal homepage: www.elsevier.com/locate/phytochem http://dx.doi.org/10.1016/j.phytochem.2017.04.023 0031-9422/© 2017 Elsevier Ltd. All rights reserved. Phytochemistry 141 (2017) 105e113