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1 Figure S1: HPLC PDA profiles (Method A, (A) full chromatogram, (B) detail): storage experiments in dark bottles filled with sage flower fluid extract at different conditions (λ at 285 nm). (1) start of storage; (2) storage over 8 months at 4 C with 100% bottle filling; (3) storage over 8 months at RT with 100% bottle filling; (4) storage over 8 months at RT with 50% bottle filling. Rosmarinic acid, 4, decreased in different intensities at the three storage conditions. Storing at 4 C carnosol, 13, decreased only a little bit and rosmanol, 9, and galdosol, 12, increased. Enhancing the storing temperature at RT this effect is more pronounced with complete reduction of carnosol, 13. Storing at RT and half bottle filling generate salviquinone A, 10, and unknown compound 13b. 1

2 Figure S2: HPLC PDA profiles (Method A, full chromatogram) of (A) fresh sage flower fluid extract and (B) a stored sage flower fluid extract in an opened vessel after one month in the dark (λ at 285 nm). Loss of solvent was corrected before analysis. Rosmarinic acid, 4, decreased after storing. Figure S3: Correlation between the yield of sage flower resin and the part of flowers on inflorescences (S. officinalis). 2

3 Figure S4: HPLC PDA profiles in detail (Method A, λ at 285 nm): Comparison of fresh petals and sepals from flowers of Salvia officinalis L. (100 mg/ml; 80% aqueous MeOH, v/v). Tri-p-coumaroylspermidine (peak 8 at min) is mainly located in the petals (-) of sage flowers. In sepals (---) 8 could not be detected. Figure S5: HPLC ELSD profiles (Method B, Gain 10) of concentrated fractions of sage flower resin (black curve) and flowers from lavender plants (red curve) with tri-p-coumaroylspermidine, 8. 3

4 Figure S6: HPLC PDA profiles (Method A, λ at 285 nm): (A) full chromatogram; (B): detail: Comparison of dried flowers from Salvia officinalis L. and Lavandulifolia augustifolia MILL. (10 mg/ml; 80% aqueous MeOH, v/v). Tri-p-coumaroylspermidine (peak 8 at 40 min) is more concentrated in lavender flowers than in sage flowers. 4

5 Figure S7: (A) ESI-MS-spectra (negative mode) and (B) UV-spectra of tri-p-coumaroylspermidine from sage flowers (1) and lavender flowers (2). Figure S8: HPLC PDA profile (semipreparative method, λ at 285 nm): Fraction collecting of 8 pre-fractions from sage flower resin dissolved in methanol. F1 include caffeic acid ethyl ester; F2 include tri-p-coumaroylspermidine; F3/4 includes salviquinone A and B; F5 include galdosol; F6 include carnosol or unknown 13b; F7/8 were not used for this work. To obtain compounds from F7/8 sage flower resin was extracted with n-pentane by Soxhlet and used for new fraction collecting experiments. 5

6 A B Figure S9: Dense packing of (2-hydro-4-isopropyl-3,6-dioxocyclohexa-1,4-dien-1-yl)-7-7-dimethyl-3-oxooctahydroisobenzofuran-1-carboxylic acid molecules (salviquinone A, 10) via hydrogen bonding interactions with the water of crystallization. Viewing directions are along [100] (A) and along [010] (B). Table S1: Major constituents of essential oils obtained by steam distillation and analyzed by GC-MS (Mean, Area%, n = 2). Peak t R (min) compounds fresh sage leaves fresh sage flowers Salvia officinalis sage flower CO 2 extract alpha-pinene 5.59 ± ± ± camphene 6.09 ± ± ± beta-pinene 2.77 ± ± ± beta-myrcen 0.56 ± ± 0.00(1) 0.08 ± para-cymen 0.14 ± ± 0.00(1) n.d ,8-cineol ± ± ± limonene 0.11 ± 0.01 n.d. n.d alpha-thujone ± ± ± beta-thujone 4.07 ± ± ± camphor ± ± ± borneol 2.34 ± ± ± ,4-terpineol 0.38 ± ± ± alpha-terpineol 0.20 ± ± ± 0.00(1) borneylacetate 1.76 ± ± ± beta-caryophyllen 2.91 ± ± ± alpha-humulen 4.01 ± ± ± caryophyllenoxid 4.60 ± ± ± 0.00(1) viridiflorol 0.32 ± ± ± manool 2.05 ± ± ± 0.29 inflorescences; n.d., not detected 6

7 Table S2: Hydrogen bonds for (2-hydro-4-isopropyl-3,6-dioxocyclohexa-1,4-dien-1-yl)-7-7-dimethyl-3-oxooctahydroisobenzofuran-1-carboxylic acid x H 2 O (salviquinone A). The oxygen and hydrogen atoms of the water of crystallization are marked with s. Symmetry codes: i: x+1/2, y+1, z+1/2; ii: x+1/2, y+1/2, z+1; iii: x, y+1/2, z+1/2. D H A d(d H) / Å d(h A) / Å <DHA / d(d A) / Å type O2 H8 O1s intermolecular O6 H24 O intramolecular O1s H2s O7 i intermolecular O2 H8 O intramolecular O1s H1s O4 ii intermolecular C15 H16 O intramolecular C19 H23 O3 iii intermolecular Table S3: X-ray crystallographic data processing and refinement statistics for (2-hydro-4-isopropyl-3,6-dioxocyclohexa-1,4-dien- 1-yl)-7-7-dimethyl-3-oxooctahydroisobenzofuran-1-carboxylic acid x H 2 O (salviquinone A). Empirical formula C 20 H 26 O 8 Formula weight g/mol Temperature 170(2) K Wavelength Å Crystal system orthorhombic Crystal habit clear orange block Crystal size x x mm Space group P Unit cell dimensions a = (3) Å α = 90 b = (5) Å β = 90 c = (8) Å γ = 90 Volume (13) Å 3 Z 4 Density (calculated) g/cm 3 Absorption coefficient mm -1 F(000) 840 Theta range for data collection to Index ranges 9 h 9, 12 k 14, 26 l 26 Reflections collected Independent reflections 3963 [R int = ] Coverage of independent reflections 99.8% Absorption correction Semi-empirical from equivalents Refinement method Full-matrix least-squares on F 2 Refinement program SHELXL-2014/7 (Sheldrick, 2014) Data / restraints / parameters 3863 / 0 / 264 Goodness-of-fit on F Final R indices 3515 data; I>2σ(I): R 1 = , wr 2 = all data: R 1 = , wr 2 = Weighting scheme w=1/[σ 2 (F 2 o )+(0.0576P) P] where P=(F 2 o +2F 2 c )/3 Largest diff. peak and hole and eå -3 7

8 Table S4: 1 H-NMR Data of isolated compounds position ferruginol (17) 20-hydroxyferruginol (15) 12-O-methyl carnosic acid (16) galdosol *1 (12) salviquinone A (10) salviquinone B (11) 1alpha td (13.3 / tdd (13.4 / ddd (13.6 / td ddd (14.1 / m 4.0) 3.8 / 1.2) 12.2 / 4.4) (13.8 / 4.4) 11.1 / 4.7) 1beta dtd (12.8 / 3.4 / 1.6) dtd (13.0 / 3.3 / 1.5) m d (14.2) ddd (14.1 / 4.3 / 4.2) dt (13.7 / 4.0) 2alpha dquin (14.0 / 3.6) dquin (14.1 / 3.5) m m dquin (14.2 / 4.5) dquin (13.7 / 4.6) 2beta qt (13.7 / qt (13.9 / m m dddt (14.2 / m 3.5) 3.2) 11.9 / 11.1 / 4.0) 3alpha td (13.5 / td (13.4 / td (12.7 / m ddd (13.6 / m 3.9) 3.8) 4.5( 11.9 / 3.9) 3beta dtd (13.2 / 3.2 / 1.5) (13.1 / 3.1 / 1.6) m m dddt (13.6 / 4.7 / 3.8 / 1.1) dt (13.3 / 4.2) dd (12.5 / dd (12.8 / dd (12.5 / s br d (8.5) br d (8.3) 2.2) 3.4) 1.9) 6alpha ddt (13.2 / dddd (13.5 / m s d (8.3) d (8.4) 7.4 / 1.8) 8.2 / 3.2 / 2.3) 6beta dddd (13.1 / tdd (13.0 / ddd (12.5 / / 11.8 / 6.7) 10.4 / 7.6) 10.3 / 7.3) 7alpha dddd (16.5 / dddd (16.8 / m / 7.3 / 0.9) 10.3 / 8.4 / 1.0) 7beta ddd (16.6 / dddd (16.8 / m / 1.5) 7.6 / 2.2 / 0.8) s s br s s s s d (1.3) br s sept (6.9) sept (6.9) sept (6.9) sept sept d (6.9 / sept (6.8) (6.9) 1.3) d (6.9) d (6.9) d (6.9) d (6.9) d (6.9) d (6.8) d (6.9) d (6.9) d (6.9) d (6.5) d (6.9) d (6.8) s s s s s s s s s s s s s d (11.1) dd (11.1 / 1.1) s s *1 measured at K 8

9 Table S5: 13 C-NMR Data of isolated compounds position ferruginol 20-hydroxyferruginol (15) 12-O-methyl carnosic acid (16) galdosol * 1 salviquinone A salviquinone B * 2 (17) (12) (10) (11) S S S M S S M M M n. d M M S S * S * S S S M S *1 measured at K, *2 carbon chemical shifts were taken from HSQC (S) or HMBC (M) spectra, *3 assignment uncertain, may be interchanged, n. d. due to low concentration, signal could not be detected Further measured data for the identification of isolated compounds from sage flower resin Compound 5 was a white powder (8.5 mg, purity by HPLC-ELSD: 100%; Method A and B). UV (mobile phase) λ max (nm) 222, 240, 298sh, 325. Negative ESI-MS: m/z 207 [M-H] -. Negative ESI-MS 2 : m/z 178, H NMR (600 MHz, CD 3 OD) δ (1H, d (15.9), C(7)H), (1H, d (2.0), C(2)H), (1H, dd (8.1 / 2.0), C(6)H), (1H, d (8.1), C(5)H), (1H, d (15.9), C(8)H), (2H, q (7.1), C(10)H2), (3H, t (7.1), C(11)H3); 13 C NMR (151 MHz, CD 3 OD): δ (C-9), (C-4), (C-3), (C-7), (C-1), (C-6), (C-5), (C-8), (C-2), 61.4 (C-10), 14.6 (C-11). In comparison to analytical standards, the compound was identified as caffeic acid ethyl ester. Compound 12 was a brown powder (18 mg, purity by HPLC-ELSD: 97.8%; Method A and B). UV (mobile phase) λ max (nm) 221, 242, 304. Negative ESI-MS: 343 [M-H] -. Negative ESI-MS 2 : 299, 243, 216. NMR-data are deposited in Table S4 and S5. Literature no.: 33,34 This compound was identified in comparison with the literature as galdosol. Compound 15 was a white amorphous powder (8.5 mg, purity by HPLC-ELSD: 98%; Method A and B). UV (mobile phase) λ max (nm) 221sh, 284. Negative ESI-MS: m/z 301 [M-H] -. NMR-data are deposited in Table S4 and S5. This compound was identified Literature no.: 35 in comparison with the literature as 20-hydroxyferruginol. Compound 16 was a colorless crystalline compound (300 mg, purity by HPLC-ELSD: 99%; Method A and B). UV (mobile phase) λ max (nm) 228sh, 282, 324. Negative ESI-MS: m/z 345 [M-H] -. Negative ESI-MS 2 : m/z 301, 286. NMR-data are deposited Literature no.: 10,36 in Table S4 and S5. This compound was identified in comparison with the literature as 12-O-methyl carnosic acid. Compound 17 was a white amorphous powder (8.5 mg, purity by HPLC-ELSD > 95%; Method A and B). UV (mobile phase) λ max (nm) 221sh, 284. Negative ESI-MS: m/z 285 [M-H] -. NMR-data are deposited in Table S4 and S5. This compound was Literature no.: 37 identified in comparison with the literature as ferruginol. 9