SUPPLEMENTARY MATERIALS
A new glucosidic phthalide from Helichrysum microphyllum subsp. tyrrhenicum
from La Maddalena Island (Sardinia, Italy)
Alessandro Vendittia,b,*, Claudia Lattanzia, Luigi Ornanoa,d, Filippo Maggic,, Cinzia Sannad,e, Mauro
Ballerod,e, Antonello Alvinoa, Mauro Serafinib, Armandodoriano Biancoa
Università di Roma “La Sapienza”, Dipartimento di Chimica, Piazzale Aldo Moro, 5 00185 Roma
a)
(Italy).
b)
Università di Roma “La Sapienza”, Dipartimento Biologia Ambientale, Piazzale Aldo Moro, 5
00185 Roma (Italy).
c)
d)
Scuola di Scienze del Farmaco e dei Prodotti della Salute, Università di Camerino.
CoSMeSe, Dipartimento di Scienze della Vita e dell’Ambiente, Università di Cagliari, Via S.
Ignazio da Laconi 11, 09123 Cagliari.
e)
Dipartimento di Scienze della Vita e dell’Ambiente, Università di Cagliari, Via S. Ignazio da
Laconi 11, 09123 Cagliari.
E-mail: alessandro.venditti@uniroma1.it
*Corresponding author. Tel. +39 0649913229; fax: +39 0649913841; E-mail address:
alessandro.venditti@uniroma1.it (A. Venditti).
Abstract
In this study we reported the analysis of the medium polarity fraction obtained from an accession of
Helichrysum microphyllum subsp. tyrrhenicum from La Maddalena Island. Besides several
compounds already evidenced in this species and related genera, i.e. micropyrone (1), arzanol (2),
helipyrone (3), acetyl-bitalin derivatives (4, 5), gnaphaliol (6), caffeic acid (7), ursolic acid (8), 7-Oβ-(D-glucopyranosyl)-5-methoxy-1(3H)-isobenzofuranone
(9),
gnaphaliol-9-O--D-
glucopyranoside (11) and gnaphaliol-3-O--D-glucopyranoside (12), was evidenced for the first
time the presence of a new glycosidic phthalide, 6-O-β-(D-glucopyranosyl)-4-methoxy-1(3H)benzofuranone (10), which resulted a structural isomer of compound (9). The occurrence of this
new benzofuranone derivative is an additional evidence of the deep intraspecific variability
expressed by this species which was also stated for the non volatile components, and may be a
distinctive trait of the population growing on La Maddalena Island.
Keywords: Helichrysum microphyllum subsp. tyrrhenicum; glycosidic phthalides; glycosidic
isobenzofuranones ; La Maddalena Island
Figure S1: 1H-NMR of compound (10).
Figure S2: 13C-NMR of compound (10).
Figure S3: Predicted
6.0.2-5475.
13
C-NMR spectrum of compound (10) on MestReNova Software version:
Figure S4: Predicted 13C-NMR spectrum of compound (10) on ACD/Labs Software (Build: 6.09/30
Sep 2002).
O
O
O
OH
O
O
OH
OH
OH
Figure S5: Observed HMBC correlation for compound (10).
Figure S6: HR-MS spectrum of compound (10).
Figure S7: HSQC correlation for compound (6) gnaphaliol.
Spectral data of isolated compounds from Helichrysum microphyllum subsp. tyrrhenicum:
micropyrone (1): 1H-NMR (400 MHz, MeOD) δ: 3.85 (1H, m, H-6), 2.58 – 2.49 (m, H-8), 1.99 (3H,
br s, H-12); 1.94 (3H, br s, H-11); 0.88 – 0.82 (3H, m, H-10).
ESI-MS: m/z 250.85 [M-H]arzanol (2): 1H NMR (300 MHz, CD3OD) δ 5.13 (1H, t, J = 6.8 Hz, H-17), 3.57 (2H, s, H-7), 3.25
(2H, d, J = 7.0 Hz,H-16), 2.67 (3H, s, H-22), 2.57 (2H, q, J = 7.5 Hz,H-12), 1.93 (3H, s, H-14), 1.75
(3H, s, H-19), 1.64 (3H, s, H-20), 1.18 (3H, t, J = 7.5 Hz, H-13).;
ESI-MS m/z 403.13 [M+H]+ ; m/z 401.07 [M-H]-.
helipyrone (3): 1H NMR (400 MHz, MeOD) δ: 3.85 (2H, s, H-9), 2.59 – 2.44 (2H, overlapped, H6), 1.88 (3H, s, H-8), 1.18 (3H, t, J = 7.0 Hz, H-7).
ESI-MS: m/z 318.79 [M-H]3-hydroxyacetyl-bitalin A (4): 1H NMR (300 MHz, CD3OD), δ: 8.07 (1H, d, J = 1.8 Hz, H-4), 7.97
(1H, dd, J = 8.5, 1.8 Hz, H-6), 6.95 (1H, d, J = 8.5 Hz, H-7), 5.27 (1H, d, J = 6.6 Hz, H-3), 5.15
(1H, d, J = 6.6 Hz, H-2), 2.57 (3H, s, H-12), 2.09 (3H, s, H-14).
ESI-MS: m/z 277.24 [M+H]+; 299.15 [M+Na]+
propanoyl-bitalin A (5): 1H NMR (300 MHz, CD3OD) δ 8.09 (1H, d, J = 1.6 Hz, H-4), 7.99 (1H,
dd, J = 8.5, 1.6 Hz, H-6), 6.97 (1H, d, J = 8.5 Hz, H7), 5.20 (1H, m, H-2), 4.54 (1H, d J = 12.2 Hz,
H9a), 4,35 (1H, d J = 12.2 Hz, H9b), 2.57 (3H, s, H-12), 2.39 – 2.23 (2H, m, H2’), 0.97 (3H, t, J =
6.8 Hz, H-3’)
ESI-MS: m/z 297.19 [M+Na]+
gnaphaliol (6): 1H-NMR (400 MHz, MeOD), δ: 8.09 (1H, d, J = 1.9 Hz, H-4), 8.00 (1H, dd, J = 8.5,
2.0 Hz, H-6), 6.97 (1H, d, J = 8.5 Hz, H-7), 5.41 – 5.37 (2H, m, H-10), 5.27 (1H, d, J = 6.4 Hz, H3), 5.21 (1H, d, J = 6.3 Hz, H-2), 4.25 (1H, d, J = 13.5 Hz, H-9a), 4.20 (1H, d, J = 13.5 Hz, H-9b),
2.57 (3H, s, H-12).
C-NMR (100 MHz, MeOD), δ: 199.9 (C11), 165.2 (C5), 143.0 (C8), 131.8 (C6), 130.9 (C5),
129.9 (C3a), 127.1 (C4), 112.5 (C10), 109.7 (C), 88.7 (C2), 71.1 (C3), 62.5 (C9), 25.1 (C12).
13
ESI-MS: m/z 257.02 [M+Na]+
caffeic acid (7): 1H NMR (300 MHz, CD3OD) δ: 7.52 (1H, d, J = 15.9 Hz, H-2), 7.31 (1H, d, J =
8.9 Hz, H-5’), 7.03 (1H, d, J = 2.0 Hz, H-2’), 6.93 (1H, dd, J = 8.9, 2.0 Hz, H-6’), 6.21 (1H, d, J =
15.9 Hz, H-2).
ESI-MS: m/z 203.10 [M+Na]+; 179.06 [M-H]ursolic acid (8): 1H NMR (300 MHz, CD3OD) δ 5.22 (1H, s, H-12), 3.22 – 3.08 (1H, m, H-3), 1.24
(6H, s, H-23;H-27), 1.09 (3H, s, H-26), 0.96 (3H, s, H-30), 0.95 (3H, d, J = 6.3 Hz, H-29), 0.93
(3H, s, H-25), 0.86 (3H, d, J = 6.5 Hz, H-30), 0.82 (3H, s, H-24).
C NMR (75 MHz, CD3OD) δ 180.3 (C28), 138.1 (C13), 125.4 (C12), 78.4 (C3), 55.3 (C5), 52.8
(C18), 47.6 (C-9), 47.5 (C-17), 41.9 (C-8; C14), 39.4 (C-4), 39.0 (C-1), 38.9 (C19), 38.6 (C20),
38.5 (C10), 36.7 (C22), 32.9 (C7), 30.5 (C21), 29.4 (C15), 27.8(C23), 27.6(C2), 25.5 (C16), 24.0
(C27), 23.0 (C30), 20.5(C26), 18.1 (C6), 16.6 (C29), 16.5 (C24), 15.2 (C25).
13
ESI-MS: m/z 479.47 [M+Na]+; 455.41 [M-H]gnaphaliol-9-O--D-glucopyranoside (11): 1H NMR (300 MHz, MeOD) δ 8.09 (1H, br s, H-4),
8.00 (1H, d, J = 8.4 Hz, H-6), 6.97 (1H, d, J = 8.5 Hz, H-7), 5.46 (2H, d, J = 4.1 Hz, H-2;H-3), 5.30
(1H, d, J = 5.6 Hz, H-10a), 5.23 (1H, d, J = 5.6 Hz, H-10b), 4.54 (1H, d, J = 12.4 Hz, H-9a), 4.35
(1H, d, J = 12.3 Hz, H-9b), 2.57 (3H, s, H-12).
ESI-MS m/z 419.14 [M+Na]+
gnaphaliol-3-O--D-glucopyranoside (12): 1H NMR (300 MHz, MeOD) δ 8.09 (1H, d, J = 1.5 Hz,
H-4), 8.00 (1H, dd, J = 8.5, 1.8 Hz, H-6), 6.98 (1H, d, J = 8.6 Hz, H-7), 5.46 (1H, d, J = 4.5 Hz, H3), 5.42 (1H, br s, H-2), 5.31 (1H, d, J = 6.5 Hz, H-10a), 5.23 (1H, d, J = 6.0 Hz, H-10b), 4.38 (1H,
d, J = 7.1 Hz, H9a), 4.29 (1H, d, J = 8.0 Hz, H-9b), 2.57 (3H, s, H-12).
ESI-MS m/z 419.14 [M+Na]+