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FULL PAPERS
Daniela Simcꢀkovꢁ et al.
50 cm, mobile phase: acetone/water/formic acid=30:1:1, v/v/
v). The fractions containing the product were pooled and
concentrated to dryness.
1H NMR in Table S4, Figure S17 in the Supporting Informa-
tion).
2-Hydroxyphenyl a-l-rhamnopyranosyl-(1!6)-b-d-gluco-
pyranoside (catechol rutinoside, 15): The reaction was per-
formed as described in the general procedure: rutin was
used as a glycosyl donor (1, 75 mg, 0.122 mmol), catechol
(80 mg, 0.727 mmol) was used as the acceptor. The title
compound 15 was isolated as a colorless amorphous solid
(TLC Rf =0.50); yield: 14.0 mg (0.033 mmol, 27.1% relative
to the donor). MS (MALDI): m/z=441.1 [M+Na]+, calcd.
mass for C18H26O11Na: 441.1 (13C NMR in Table S2, Fig-
Ethyl a-l-rhamnopyranosyl-(1!6)-b-d-glucopyranoside
(ethyl rutinoside, 9): The reaction was performed as de-
scribed in the general procedure, ethanol (3 mL, 51.3 mmol)
was used as the acceptor. 9 was isolated as a colorless amor-
phous solid (TLC Rf =0.37); yield: 34.7 mg (0.098 mmol,
46.0% relative to the donor). MS (ESI): m/z=377.0 [M+
Na]+, calcd. mass for C14H26O10Na: 377.1 (13C NMR in
1
Table S2, Figure S6; H NMR in Table S3, Figure S7 in the
1
ure S18; H NMR in Table S4, Figure S19 in the Supporting
Supporting Information).
Information).
n-Butyl a-l-rhamnopyranosyl-(1!6)-b-d-glucopyranoside
(n-butyl rutinoside, 10): The reaction was performed as de-
scribed in the general procedure, n-butanol (750 mL,
8.16 mmol) was used as an acceptor. 10 was isolated as a col-
orless amorphous solid (TLC Rf =0.56); yield: 37.7 mg
(0.095 mmol, 44.6% relative to the donor). MS (MALDI):
m/z= 405.1 [M+Na]+, calcd. mass for C16H30O10Na: 405.2
5,4’-Trihydroxy-trans-stilbene-3-yl-[a-l-rhamnopyranosyl-
(1!6)-b-d-glucopyranoside] 16a and 3,5-trihydroxy-trans-
stilbene-4’-yl-[a-l-rhamnopyranosyl-(1!6)-b-d-glucopyra-
noside] 16b (resveratrol rutinoside): The reaction was per-
formed as described in the general procedure: rutin was
used as a donor (1, 130 mg, 0.213 mmol), resveratrol (60 mg,
0.263 mmol) as an acceptor. Product 16 was isolated as a col-
orless amorphous solid (TLC Rf =0.45); yield: 9.3 mg
(0.017 mmol, 8.0% relative to the donor). NMR showed
that the product consists of an (inseparable) mixture of two
compounds 16a and 16b in the ratio 2:1 (C-3 and C-4’ glyco-
sides). MS (ESI): m/z=535.2 [MꢀH]ꢀ, calcd. mass for
C26H31O12: 535.2 (13C NMR in Table S5, Figure S20;
1H NMR in Table S5, Figure S21 in the Supporting Informa-
tion).
1
(13C NMR in Table S2, Figure S8; H NMR in Table S3, Fig-
ure S9 in the Supporting Information).
Pentan-2-yl a-l-rhamnopyranosyl-(1!6)-b-d-glucopyra-
noside (pentan-2-yl rutinoside, 11): The reaction was per-
formed as described in the general procedure, pentan-2-ol
(750 mL, 6.91 mmol) was used as an acceptor. 11 was isolat-
ed as a colorless amorphous solid (TLC Rf =0.60); yield:
32 mg (0.081 mmol, 37.9% relative to the donor). MS
(MALDI): m/z=419.1 [M+Na]+, calcd. mass for
C17H32O10Na: 419.2 (13C NMR in Table S2, Figure S10;
1H NMR in Table S3, Figure S11 in the Supporting Informa-
tion).
Acknowledgements
(E)-3,7-Dimethylocta-2,6-dien-1-yl [a-l-rhamnopyranosyl-
(1!6)-b-d-glucopyranoside] (geranyl rutinoside, 12): The
reaction was performed as described in the general proce-
dure: rutin was used as the donor (1, 130 mg, 0.213 mmol)
and geraniol (700 mL, 4.03 mmol) was used as the acceptor.
The title compound 12 was isolated as a colorless amor-
phous solid (TLC Rf =0.63); yield: 4.0 mg (9 mmol, 4.1% rel-
ative to the donor). MS (ESI): m/z=485.3 [M+Na]+, calcd.
mass for C22H38O10Na: 485.2 (13C NMR in Table S2, Fig-
Support from the EU project NOVOSIDES FP7-KBBE-
2010-4-265854 and from projects from the Czech Ministry of
Education (LD13042 and 7E11011) is acknowledged.
˚
Thanks are due to Dr. Z. Voburka (Institute of Organic
Chemistry and Biochemistry, Academy of Sciences of the
Czech Republic, Prague) for the aminoacid Edman analyses,
Dipl.-Ing. Petr Marhol (Institute of Microbiology, Prague)
ˇ
for HPLC analysis and Dr. M. Sulc (Institute of Microbiolo-
1
ure S12; H NMR in Table S3, Figure S13 in the Supporting
gy, Prague) for MALDI-MS measurements.
Information).
Cyclohexyl a-l-Rhamnopyranosyl-(1!6)-b-d-glucopyra-
noside (cyclohexyl rutinoside, 13): The reaction was per-
formed as described in the general procedure: rutin was
used as a donor (1, 130 mg, 0.213 mmol), cyclohexanol
(700 mL, 6.73 mmol) as the acceptor. The title compound 13
was isolated as a colorless amorphous solid (TLC Rf =0.27);
yield: 19.3 mg (0.047 mmol, 22.2% relative to the donor).
MS (ESI): m/z=431.1 [M+Na]+, calcd. mass for
C18H32O10Na: 431.2 (13C NMR in Table S2, Figure S14;
1H NMR in Table S4, Figure S15 in the Supporting Informa-
tion).
Benzyl a-l-rhamnopyranosyl-(1!6)-b-d-glucopyranoside
(benzyl rutinoside, 14): The reaction was performed as de-
scribed in the general procedure, benzylalcohol (450 mL,
4.32 mmol) was used as the acceptor. The title compound 14
was isolated as a colorless amorphous solid (TLC Rf =0.55);
yield: 16.1 mg (0.039 mmol, 18.2% relative to the donor).
MS (MALDI): m/z=439.1 [M+Na]+, calcd. mass for
C19H28O10Na: 439.1 (13C NMR in Table S2, Figure S16;
References
[1] L. Zhou, C. Lu, G. L. Wang, H. L. Geng, J. W. Yang, P.
Chen, J. Asian. Nat. Prod. Res. 2009, 11, 18.
[2] M. F. Iqbal, W. Y. Zhu, FEMS Microbiol. Lett. 2009,
295, 30.
[3] L. Mazzaferro, L. Pinuel, M. Minig, J. D. Breccia, Arch.
Microbiol. 2010, 192, 383.
[4] M. Minig, L. S. Mazzaferro, R. Erra-Balsells, G. Petro-
selli, J. D. Breccia, J. Agric. Food Chem. 2011, 59,
11238.
[5] S. Katayama, F. Ohno, Y. Yamauchi, M. Kato, H.
Makabe, S. Nakamura, J. Agric. Food Chem. 2013, 61,
9617.
[6] L. S. Mazzaferro, J. D. Breccia, Biocatal. Biotransform.
2011, 29, 103.
[7] M. A. Robinson, S. T. Charlton, P. Garnier, X. Wang,
S. S. Davis, A. C. Perkins, M. Frier, R. Duncan, T. J.
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ꢂ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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