Contents lists available at ScienceDirect Biochemical Systematics and Ecology journal homepage: www.elsevier.com/locate/biochemsyseco Natural products from Tolpis barbata (L.) Gaertn. (Asteraceae, Cichorieae) Klaudia Michalska a , Janusz Malarz a , Wojciech Paul b , Anna Stojakowska a,* a Maj Institute of Pharmacology, Polish Academy of Sciences, Department of Phytochemistry, 31-343, Kraków, 12 Smętna Street, Poland b W. Szafer Institute of Botany, Polish Academy of Sciences, 31-512, Kraków, 46 Lubicz Street 46, Poland ARTICLEINFO Keywords: Asteraceae Benzopyrans Phenolics Sesquiterpene lactone Tolpis barbata ABSTRACT One sesquiterpene lactone – 9α-hydroxy-3-deoxyzaluzanin C, three benzopyrans: desmethoxyencecalin (6- acetyl-2,2-dimethylchromene), desacetylripariochromen B and 6-(1-hydroxyethyl)-2,2-dimethylchromene, one coumarin – scopoletin and two eugenol derivatives were isolated from the roots of Tolpis barbata (L.) Gaertn, hitherto unexamined species. In the extract from aerial parts of the plant, five known phenolic compounds, namely: esculin, esculetin, chlorogenic acid (5-CQA), luteolin 7-O-glucoside and 3,5-dicaffeoylquinic acid (3,5- DCQA) were identified as major constituents. Except for the two coumarins – scopoletin and esculetin, which were previously obtained from Tolpis webbii Sch.Bip. and T. proustii Pit., the isolated and identified compounds have not been previously reported as constituents of Tolpis spp. Though benzopyrans were found in numerous species of the Asteraceae, their occurrence in the tribe Cichorieae has not been demonstrated before. 1. Subject and source The genus Tolpis,whichbelongstothetribeCichorieaeofthefamily Asteraceae, includes approximately 12–20 species, distributed in Europe,MiddleEastandNorthernAfrica(Parketal.,2001).Majorityof the known Tolpis species are Macaronesian endemites and only two (T. barbata and T. virgata (Desf.) Bertol.) are regarded as continental spe- cies. In contrast to the endemic species, T. barbata is an annual her- baceous plant with white corollas on the outer florets of capitula. The endemites are usually woody perennials (except for T. coronopifolia (Desf.) Biv.), and their capitula have uniformly yellow corollas (Moore et al., 2002; Kerbs et al., 2017). Roots and aerial parts of T. barbata were collected separately, on 12 July 2016, from the plants grown in the Garden of Medicinal Plants of the Institute of Pharmacology, Polish Academy of Sciences, Kraków, Poland, where a voucher specimen (2/2016) was deposited. Seeds of the plant were supplied by the Botanical Garden of the University of Konstanz, Germany (accession number: 9711826) and were originally collected in Sorede (Roussillon, France). The plant identity was con- firmed by one of the authors (WP, a plant taxonomist). 2. Previous work According to ethnobotanical studies, T. barbata is one of the five most popular wild growing plants consumed in Spain (Hadjichambis et al., 2008). However, we could not find any report on chemical constituents of the plant. Data on specialized metabolites produced by the plants of Tolpis spp. are scanty. To our knowledge, only three Ma- caronesianspecies,i.e.: T. webbii Sch.Bip., T. proustii Pit.and T. lagopoda C.Sm. ex Link as well as one unidentified Tolpis sp. collected in La Palma (Canary Islands) have been phytochemically investigated so far (Triana et al., 2009, 2012). From aerial parts of the examined plants numerous triterpenes and sterols, including five new compounds, were isolated. The only phenolic compound found in T. lagopoda and Tolpis sp. was 2,4′-dihydroxy-4-methoxybenzophenone. The metabolite was also found in T. webbii together with vanillin and scopoletin. Aerial parts of T. proustii contained scopoletin, apigenin and esculetin. The lattercompound,basedonisolationyields,wasthemajorconstituentof theplantmaterialunderinvestigation.Asfarasweareaware,thereare noreportsonsesquiterpenelactonesin Tolpis spp.Thesecompoundsare important chemotaxonomic markers within the Asteraceae and common constituents of the Cichorieae (Zidorn, 2008; Shulha and Zidorn, 2019). 3. Present study The present communication deals with the isolation of seven known compounds (1–7, Fig. 1), including one sesquiterpene lactone, from roots of T. barbata and with the identification of five major phenolic compounds (8–12, Fig. 1) present in the aerial parts. https://doi.org/10.1016/j.bse.2019.103922 Received 28 May 2019; Received in revised form 2 July 2019; Accepted 4 July 2019 * Corresponding author. E-mail address: stoja@if-pan.krakow.pl (A. Stojakowska). Biochemical Systematics and Ecology 86 (2019) 103922 0305-1978/ © 2019 Published by Elsevier Ltd. T