Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
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
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
-
References and Notes
- 1a Bililign T, Griffith BR, Thorson JS. Nat. Prod. Rep. 2005; 22: 742
- 1b Hultin PG. Curr. Top. Med. Chem. 2005; 5: 1299
- 1c Rauter AP, Lopes RG, Martins A. Nat. Prod. Commun. 2007; 11: 1175
- 1d Wang Q, Shuang A, Deng Z, Zhu W, Huang Z, Gang H, Chen G. Nat. Catal. 2019; 2: 793
- 1e Xiao J, Capanoglu E, Jassbi AR, Miro A. Crit. Rev. Food Sci. Nutr. 2016; 56: S29
- 2a Rawat P, Kumar M, Sharan K, Chattopadhyay N, Maurya R. Bioorg. Med. Chem. Lett. 2009; 19: 4684
-
2b
Maurya R,
Rawat P,
Sharan K,
Siddiqui JA,
Swarnkar G,
Mishra G,
Manickavasagam L,
Jain GK,
Arya KR,
Chattopadhyay N.
PCT Patent PCT/IN2009/000146, 2009; (WO2009110003A1, WO200911000, 2009
- 2c Stark TD, Germann D, Balemba OB, Wakamatsu J, Hofmann T. J. Agric. Food Chem. 2013; 61: 12572
-
2d
Sabyasachi S,
Chattopadhyay N,
Maurya R,
Gayen JR,
Bhadauria S,
Trivedi AK,
Singh AK,
Mishra JY,
Kumari R,
Sharan K,
Khan MP,
Khan K,
Singh N,
Dwivedi SK. D,
Yadav M,
Dixit P,
Mishra DP,
Sharma S,
Kamal RA.
PCT Patent PCT/IN2014/000464, 2014; (US2016/019324, 2014
- 2e Gupta P, Singh A, Tiwari S, Mishra A, Maurya R, Singh S. Neurotoxicology 2019; 73: 100
- 3a Stark T, Matsutomo T, Losch S, Boakye P, Balemba O, Pasilis S, Hofmann T. J. Agric. Food Chem. 2012; 60: 2053
- 3b Mbafor JT, Fomum ZT, Promsattha B, Sanson DR, Tempesta MS. J. Nat. Prod. 1989; 52: 417
- 4a Jaramilo C, Knapp S. Synthesis 1994; 1
- 4b Levy DE, Tang C. The Chemistry of C-Glycosides. Pergamon; Oxford: 1995
- 4c Postema MH. D. C-Glycoside Synthesis. CRC Press; London: 1995
- 4d Du Y, Linhardt RJ. Tetrahedron 1998; 54: 9913
- 4e Toshima K, Matsuo G, Nakata M, Matsumura S. J. Synth. Org. Chem. Jpn. 1998; 56: 841
- 4f Schmidt RR, Hoffmann M. Tetrahedron Lett. 1982; 23: 409
- 5 Matsumoto T, Katsuki M, Suzuki K. Tetrahedron Lett. 1988; 29: 6935
- 6 Kometani T, Kondo H, Fujimori Y. Synthesis 1988; 1005
- 7a Sato S, Akiya T, Nishizawa H, Suzuki T. Carbohydr. Res. 2006; 341: 964
-
7b
Van Der Westhuizen JH,
Ferreira D,
Joubert E,
Bonnet SL.
WO2011064726A1, 2011
- 7c Sato S, Koide T. Carbohydr. Res. 2010; 345: 1825
- 8 Santos RG, Xavier NM, Bordado JC, Rauter AP. Eur. J. Org. Chem. 2013; 1441
- 9a Kitamura K, Ando Y, Matsumoto T, Suzuki K. Chem. Rev. 2018; 118: 1495
- 9b Yang Y. Yu B. 2017; 117: 12281
- 10a Park KD, Cho SJ. Eur. J. Med. Chem. 2010; 45: 1028
- 10b Es-Safi N.-E, Ducrot P.-H. Lett. Org. Chem. 2006; 3: 231
- 10c Kikuchi T, Nishimura M, Hoshino A, Mortia Y, Saito N, Honda T. Heterocycles 2003; 60: 1469
- 11 Yang LX, Huang KX, Li HB, Gong JX, Wang F, Feng YB, Tao QF, Wu YH, Li XK, Wu XM, Zeng S, Spencer S, Zhao Y, Qu J. J. Med. Chem. 2009; 52: 7732
- 12 Wu Z, Wei G, Lian G, Yu B. J. Org. Chem. 2010; 75: 5725
-
13
Rao BV,
Lingamurthy M,
Raju G,
Sarma VU. M.
US20160362401A1, 2016; (US9611255B2)
-
14
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]+.