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Synlett 2020; 31(11): 1097-1101
DOI: 10.1055/s-0040-1707971
DOI: 10.1055/s-0040-1707971
letter
Total Synthesis of the Natural Products Ulmoside A and (2R,3R)-Taxifolin-6-C-β-d-glucopyranoside
Authors
M.L.M and G.R. thank the Council of Scientific and Industrial Research (CSIR). A.R.D thanks the University Grants Commission (UGC), New Delhi for financial support as part of XII Five Year Plan programme under the titles ORIGIN (CSC-0108) and DENOVA (CSC-0205); Manuscript communication number: IICT/Pubs./2019/342.
Further Information
Publication History
Received: 04 February 2020
Accepted after revision: 19 February 2020
Publication Date:
02 March 2020 (online)
# Both authors contributed equally.
Abstract
An efficient first total synthesis of highly polar ulmoside A and (2R,3R)-taxifolin-6-C-β-d-glucopyranoside, useful for the prevention of metabolic disorders, has been described. Key elements of the synthesis include a Sc(OTf)3-catalyzed regio- and stereoselective C-glycosidation on taxifolin in 35% yield with d-glucose and chiral semipreparative reverse-phase high-performance liquid chromatography (HPLC) for the separation of both taxifolins and the diastereomeric mixture of taxifolin-6-C-β-d-glucopyranosides. Correlation of the analytical data of synthetic ulmoside A and its diastereomer with a natural ulmoside A sample confirmed the assigned absolute stereochemistry of the natural products.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707971.
- Supporting Information (PDF)
-
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Ulmoside A (1)A solution of (–)-taxifolin (4) (0.3 g, 0.98 mmol) and d-glucose (0.44 g, 2.46 mmol) was stirred in a mixture of solvents MeCN/H2O (2:1, 10 mL) heated to reflux in an oil bath for 48 h in the presence of Sc(OTf)3 (0.19 g, 0.39 mmol). Then, the reaction mixture was subjected to silica gel column
chromatography (acetone/EtOAc/H2O/AcOH 15:30:2:0.1) to afford ulmoside A (1) as a white amorphous powder yield: 0.16 g (35%); [α]D
25 = +1.56 (c = 0.1, MeOH){lit2a[α]D
25 = +1.33 (c = 0.098, MeOH)}. IR (neat): 3325, 2945, 2833, 1646, 1450, 1413, 1017 cm–1. 1H NMR (500 MHz, DMSO-d
6): δ = 12.47 (s, 1 H, HO-C(5)), 9.03 (s, 1 H, HO-C(4')), 8.98 (s, 1 H, HO-C(3')),
6.84 (s, 1 H, H-2'), 6.71 (s, 2 H, H-5', 6'), 5.87 (s, 1 H, H-8), 5.78 (s, 1 H, HO-C(3)),
4.92 (d, J = 10.9 Hz, 1 H, H-2), 4.82 (br s, 2 H, OH), 4.58 (br s, 1 H, OH), 4.46–4.47 (m, 1
H, H-6''b), 4.45 (d, J = 10.0 Hz, 1 H, H-1''), 4.43 (d, J = 10.9 Hz, 1 H, H-3), 3.96 (t, J = 9.1, 9.3 Hz, 1 H, H-2''), 3.63 (d, J = 10.9 Hz, 1 H, H-6''a), 3.04–3.15 (m, 3 H, H-3'', 4'', 5''). 13C NMR (125 MHz, DMSO-d
6): δ = 198.0 (C-4), 166.0 (C-7), 162.6 (C-5), 161.3 (C-9), 145.8 (C-3'), 145.0 (C-4'), 128.0
(C-1'), 119.4 (C-6'), 115.3 (C-2'), 115.1 (C-5'), 106.0 (C-6), 100.2 (C-10), 94.7
(C-8), 82.9 (C-2), 81.6 (C-5''), 79.1 (C-3''), 72.9 (C-1''), 71.6 (C-3), 70.7 (C-2''),
70.3 (C-4''), 61.6 (C-6''). FAB-MS: m/z 467 [M + H]+.
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