2From an extract of Veronica (sect. Hebe) lavaudiana we have identified mannitol and isolated 11 iridoid glucosides, the carbohydrate ester hebitol II, and four phenylethanoid glycoside esters. Five of the iridoid glycosides are new; of these, lavaudioside A, B, and C (2a, 3a, and 4) are 1-mannityl esters of 8-epiloganic acid while 7e and 7f are 6'-O-caffeoyl derivatives of catalpol. The new phenylethanoid glycoside esters, helioside A, B, and C (8b-8d), are 6'-xylosyl derivatives of aragoside. The structures of the new compounds were elucidated mainly by spectroscopic analysis, but also by chemical degradation.We also demonstrated that the structures of the known glycosides globularitol as well as hebitols I and II should be revised. These compounds are derivatives of mannitol and not glucitol as previously believed.3 Veronica (sect. Hebe) lavaudiana Raoul is an endemic subshrub that grows on basalt outcrops and cliffs above 150 m altitude on Banks Peninsula on the east coast of the South Island of New Zealand. 1 The peninsula, reaching an altitude of about 900 m, is formed from two extinct volcanoes and has at times in the past been separated as an island. V. lavaudiana and its nearest relatives in the sect. Hebe belong in the sun hebe clade. 2 It has been formerly treated as the genus Heliohebe 1 or as part of Hebe 3 or Parahebe, 4 all of which are now included in a broad and monophyletic concept of Veronica. 5 Little chemical work has been undertaken on V. lavaudiana. Thus, this species was included in an early chemotaxonomic survey of iridoids and flavonoids in Veronica and related genera, 6 and in a recent LC/MS investigation on the flavonoid chemistry of the five species of Heliohebe. 7 Fresh plant material was blended with cold MeOH and the water-soluble part of the extract was subjected to a series of chromatographic procedures. Seventeen compounds were isolated and identified including the hexitol, mannitol (1), the carbohydrate ester hebitol II (5), 11 iridoid glucosides (2a, 3a, 4, 6, 7-7f), and four phenylethanoid glycoside esters (8, 8b-8d). Of these, the five iridoids 2a, 3a, 4, 7e, 7f and the three phenylethanoids 8b-8d are new.The composition of the sugar fraction was deduced by interpretation of the 13 C NMR data only. present. Also, two β-hexopyranosyl groups were considered present due to the two doublets at δ H 4.69 and 4.36. In the 13 C NMR spectrum (Table 1) of 4, 39 resonances were observed, of which five were of double and one (δ C 71.6) was of triple intensity, as also confirmed by the HSQC data. Eighteen of the resonances could be assigned to the two caffeoyl groups and comparing with the data for 2a, a further 16 could be assigned to an epiloganyl moiety including its 1-O-glucosyl group. This left 12 13 C NMR resonances to be accounted for. That at δ C 105.0 was assigned to an anomeric carbon atom and the remaining 11, resonating at δ C 64-78, suggested the presence of a hexopyranosyl and a hexityl moiety.2D NMR data suggested that the hexopyranosyl moiety was an additional β-glucopyr...