SUPPLEMENTARY MATERIAL
A new hemiterpene glycoside from the ripe tomatoes
Masateru Onoa,*, Shin Yasudaa, Yuki Shionoa, Chisato Furusawaa, Shinya
Inabaa, Takayuki Tanakaa, Tsuyoshi Ikedab and Toshihiro Noharab
a
School of Agriculture, Tokai University, Minamiaso 5435, Aso, Kumamoto 869-
1404, Japan; bFaculty of Pharmaceutical Sciences, Sojo University, 4-22-1 Ikeda,
Nishi-ku, Kumamoto 860-0082, Japan
*Corresponding author: E-mail: mono@agri.u-tokai.ac.jp
Abstract
A new hemiterpene glycoside (1) was isolated from ripe tomatoes (the fruit of Lycopersicon
esculentum, Solanaceae) along with eight known compounds. The chemical structure of 1 was
determined to be 2-methylbutan-1-ol -D-glucopyranosyl-(1→6)--D-glucopyranoside, based
on spectroscopic data as well as chemical evidence. In addition, the radical-scavenging
activities of the isolated compounds on the free radical of 1,1-diphenyl-2-picrylhydrazyl were
examined. Among the tested compounds, tryptophan, 4-O--D-glucopyranosyl caffeic acid,
and dihydro-p-coumaryl alcohol -O--D-glucopyranoside demonstrated 42.0%, 50.1%, and
76.0% scavenging activities, respectively, at a concentration of 0.5 mM.
Table S1. 1H- and 13C-NMR spectral data for 1 (in pyridine-d5)
H
Agl-1a
Agl-1b
Agl-2
Agl-3a
Agl-3b
Agl-4
Agl-5
Glc-1
Glc-2
Glc-3
Glc-4
Glc-5
Glc-6a
Glc-6b
Glc'-1
Glc'-2
Glc'-3
Glc'-4
Glc'-5
Glc'-6a
Glc'-6b
*
4.08
3.99 dd(6.5, 9.5)
1.72 m
1.51 m
1.11 m
0.80 t(7.5)
0.94 d(7.0)
4.76 d(8.0)
4.00 dd(8.0, 8.5)
4.21 dd(8.5, 8.5)
4.16 dd(8.5, 8.5)
4.11 m
4.87 dd(1.5, 11.5)
4.36 dd(6.5, 11.5)
5.15 d(7.5)
4.06*
4.26*
ca. 4.27
3.95 m
4.54 dd(1.5, 12.0)
4.39 dd(4.5, 12.0)
C
75.0
35.4
26.4
11.4
16.8
104.9
75.1
78.5
71.8
77.3
70.2
105.5
75.3
78.5
71.7
78.5
62.8
 in ppm from TMS (coupling constants (J) in Hz are given
in parentheses). Agl, aglycone moiety. Glc, inner glucosyl
group. Glc', terminal glucosyl group. *, Signals were
overlapping. 1H-NMR spectral data (500 MHz). 13C-NMR
spectral data (125 MHz).
Table S2. 1H- and 13C-NMR spectral data for 8 (in pyridine-d5)
H
Agl-1a
Agl-1b
Agl-2a
Agl-2b
Agl-3
Agl-4a
Agl-4b
Agl-5
Agl-6a
Agl-6b
Agl-7a
Agl-7b
Agl-8
Agl-9
Agl-10
Agl-11a
Agl-11b
Agl-12a
Agl-12b
Agl-13
Agl-14
Agl-15a
Agl-15b
Agl-16
Agl-17
Agl-18
Agl-19
Agl-20
Agl-21
Agl-22
C
1.48*
0.79*
2.06 m
1.61*
3.94*
1.81*
1.40*
0.90*
1.14*
1.09*
1.50*
0.81*
1.27*
0.51 ddd(2.5, 8.5, 8.5)
1.37*
1.11*
1.65*
1.00 m
37.2
29.8
78.7
34.8
44.6
28.8
32.3
34.9
54.5
35.8
20.7
38.2
41.8
0.92
54.5
2.17 ddd(6.5, 7.5, 14.0) 33.2
1.39*
4.99 ddd(4.5, 7.5, 7.5) 82.7
1.84 br d(7.5)
59.0
0.70 s
13.8
0.62 s
12.2
2.70 q(7.5)
36.3
1.31 d(7.5)
17.9
181.1
*
H
Gal-1
Gal-2
Gal-3
Gal-4
Gal-5
Gal-6a
Gal-6b
Glc-1
Glc-2
Glc-3
Glc-4
Glc-5
Glc-6a
Glc-6b
Glc'-1
Glc'-2
Glc'-3
Glc'-4
Glc'-5
Glc'-6a
Glc'-6b
Xyl-1
Xyl-2
Xyl-3
Xyl-4
Xyl-5a
Xyl-5b
4.90 d(7.5)
4.41 dd(7.5, 9.5)
4.18*
4.61 d(3.5)
4.05*
4.64 dd(8.5, 11.0)
4.23*
5.15 d(8.0)
4.34 dd(8.0, 8.5)
4.11 dd(8.5, 8.5)
3.78 dd(8.5, 8.5)
3.85*
4.49 dd(1.5, 10.0)
4.03*
5.54 d(7.5)
4.07 dd(7.5, 8.5)
4.09*
4.17*
3.93*
4.52 dd(1.5, 10.5)
4.37*
5.19 d(8.0)
3.95 dd(8.0, 8.5)
4.18*
4.12*
4.23*
3.68 dd (10.5, 10.5)
C
102.4
73.2
75.4
79.9
75.6
60.6
105.1
81.3
86.8
70.5
77.3
63.0
104.8
76.2
77.6
71.1
77.8
62.5
104.9
75.1
78.6
70.7
67.3
 in ppm from TMS (coupling constants (J) in Hz are given in parentheses). Agl,
aglycone moiety. Gal, galactosyl group. Glc, inner glucosyl group. Glc', terminal
glucosyl group. Xyl, Xylosyl group. *, Signals were overlapping. 1H-NMR spectral
data (500 MHz). 13C-NMR spectral data (125 MHz).
Figure S1. Connectivities elucidated by the 1H-1H COSY spectrum (bold lines) and
1
H-13C long-range correlations (arrows) observed in the HMBC spectrum of 1 (in
pyridine-d5, 500 MHz)
Trolox
3
4
6
0
20
40
60
80
100
Scavenging Effect (%)
Figure S2. DPPH radical-scavenging effects of 3, 4, 6, and Trolox. Data shown
represent mean ± S.D. derived from four determinations. The final concentration of
each sample tested was 0.5 mM.
Figure S3. 1H-NMR spectrum of 1 (in pyridine-d5, 500 MHz)
Figure S4. 13C-NMR spectrum of 1 (in pyridine-d5, 125 MHz)
Figure S5. 1H-1H COSY spectrum of 1 (in pyridine-d5, 500 MHz)
Figure S6. HMQC spectrum of 1 (in pyridine-d5, 500 MHz)
Figure S7. HMBC spectrum of 1 (in pyridine-d5, 500 MHz)
Figure S8. Positive FAB-MS of 1
Figure S9. Positive FAB-MS of 1
Figure S10. 1H-NMR spectrum of 8 (in pyridine-d5, 500 MHz)
Figure S11. 13C-NMR spectrum of 8 (in pyridine-d5, 125 MHz)
Figure S12. 1H-1H COSY spectrum of 8 (in pyridine-d5, 500 MHz)
Figure S13. HMQC spectrum of 8 (in pyridine-d5, 500 MHz)
Figure S14. HMBC spectrum of 8 (in pyridine-d5, 500 MHz)