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
Download PDF
Synlett 2020; 31(11): 1083-1086
DOI: 10.1055/s-0040-1708021
DOI: 10.1055/s-0040-1708021
letter
Practical Synthesis of the Fluorogenic Enzyme Substrate 4-Methylumbelliferyl α-l-Idopyranosiduronic Acid
Authors
This project was supported by the National Natural Science Foundation of China (Grant No. 21676131, 21462019), the Bureau of Science & Technology of Jiangxi Province (Grant No. 20143ACB20012), the Education Department of Jiangxi Province (Grant No.170673), and the Jiangxi Science & Technology Normal University (Doctor Startup Fund 2018BSQD022).
Further Information
Publication History
Received: 03 March 2020
Accepted after revision: 27 March 2020
Publication Date:
17 April 2020 (online)
Abstract
A practical and concise synthesis of 4-methylumbelliferyl α-l-idopyranosiduronic acid, a fluorogenic enzyme substrate diagnostic for α-l-iduronidase, was accomplished. It features successive radical bromination and radical reduction of easily accessible methyl 4-methylumbelliferyl-2,3,4-tri-O-acetyl-β-d-glucouronate in four steps with 28% overall yield.
Key words
α-l-Iduronidase - 4-methylumbelliferyl α-l-idopyranosiduronic acid - radical reduction - radical bromination - fluorogenic enzyme substrate - synthesisSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1708021.
- Supporting Information (PDF)
-
References and Notes
- 1a Clements PR, Muller V, Hopwood JJ. Eur. J. Biochem. 1985; 152: 29
- 1b Freeman C, Hopwood JJ. Biochem. J. 1992; 282: 899
- 2a Muenzer J, Wraith JE, Clarke LA. Pediatrics 2009; 123: 19
- 2b Campos D, Monaga M. Metab. Brain Dis. 2012; 27: 121
- 3a Archer LD, Langford-Smith KJ, Bigger BW, Fildes JE. J. Inherited Metab. Dis. 2014; 37: 1
- 3b Parini R, Deodato F, Di RM, Lanino E, Locatelli F, Locatelli F, Messina C, Rovelli A, Scarpa M. Orphanet J. Rare Dis. 2017; 12: 112
- 4a Scott HS, Bunge S, Gal A, Clarke LA, Morris CP, Hopwood JJ. Hum. Mutat. 1995; 6: 288
- 4b Langereis EJ, van Vlies N, Wijburg FA. Expert Opin. Orphan Drugs 2015; 3: 307
- 5a Burke HM, Gunnlaugsson T, Scanlan EM. Chem. Commun. 2015; 51: 10576
- 5b Turunen P, Rowan AE, Blank K. FEBS Lett. 2014; 588: 3553
- 5c Grimm JB, Heckman LM, Lavis LD. Prog. Mol. Biol. Transl. Sci. 2013; 113: 1
- 5d Wysocki LM, Lavis LD. Curr. Opin. Chem. Biol. 2011; 15: 752
- 6a Utterworth J, Broadhead DM. J. Inherited Metab. Dis. 1979; 2: 71
- 6b Hopwood JJ, Muller V, Smithson A, Baggett N. Clin. Chim. Acta 1979; 92: 257
- 6c Butterworth J, Broadhead DM. J. Inherit. Metab. Dis. 1980; 2: 71
- 6d Breier AC, Ce J, Mezzalira J, Daitx VV, Moraes VC, Goldim MP. S, Coelho JC. Clin. Biochem. 2017; 50: 431
- 6e Ou L, Herzog TL, Wilmot CM, Whitley CB. Mol. Genet. Metab. 2014; 111: 113
- 7a Srivastava RM, Hudson N, Seymour FR, Weissmann B. Carbohydr. Res. 1978; 60: 315
- 7b Weissmann B. Methods Enzymol. 1978; 50: 141
- 8a Voznyi YV, Kalicheva IS, Galoyan AA, Gusina NB. Bioorg. Khim. 1989; 15: 1411
- 8b Voznyi YV, Kalicheva IS, Galoyan AA. Bioorg. Khim. 1987; 13: 1655
- 9a Lu FC, Lico LS, Hung SC. ARKIVOC 2013; (ii): 13
- 9b Lee J.-C, Chang SW, Liao CC, Chi FC, Chen CS, Wen YS, Wang CC, Kulkarni SS, Puranik R, Liu YH, Hung SC. Chemistry 2004; 10: 399
- 10 Tian JM, Ning QQ, Ding HX, Bai J, Xiao Q. Chin. J. Org. Chem. 2020; 40: 215
- 11a Zulueta MM. L, Zhong YQ, Hung SC. Chem. Commun. 2013; 49: 3275
- 11b Lee JC, Chang SW, Liao CC, Chi FC, Chen CS, Wen YS, Wang CC, Kulkarni SS, Puranik R, Liu YH, Hung SC. Chem. Eur. J. 2004; 10: 399
- 11c Pellissier H. Org. Prep. Proced. Int. 2002; 34: 441
- 12 Cheallaigh AN, Potter GT, Gardiner JM, Miller GJ. Org. Synth. 2016; 93: 200
- 13a Mikula H, Matscheko D, Schwarz M, Hametner C, Froehlich J. Carbohydr. Res. 2013; 370: 19
- 13b Chen DZ, Wu T, Zhao Z, Lin XQ, Yang T, Yang J. J. Chem. Res. 2013; 37: 671
- 14a Nasseri SA, Betschart L, Opaleva D, Rahfeld P, Withers SG. Angew. Chem. Int. Ed. 2018; 57: 11359
- 14b Anderson FB. Clin. Chim. Acta 1965; 12: 669
- 15a Ferrier RJ, Furneaux RH. J. Chem. Soc., Perkin Trans. 1 1977; 1996
- 15b Chiba T, Sinay P. Carbohydr. Res. 1986; 151: 379
- 15c Somsak L, Ferrier RJ. Adv. Carbohydr. Chem. Biochem. 1991; 49: 37
- 15d Yu HN, Furukawa J, Ikeda T, Wong CH. Org. Lett. 2004; 6: 723
- 16a Cao X, Lv Q, Li D, Ye H, Yan X, Yang X, Gan H, Zhao W, Jin L, Wang P, Shen J. Asian J. Org. Chem. 2015; 4: 899
- 16b Mohamed S, Krenske EH, Ferro V. Org. Biomol. Chem. 2016; 14: 2950
- 16c Pawar NJ, Wang L, Higo T, Bhattacharya C, Kancharla PK, Zhang FM, Baryal K, Huo CX, Liu J, Linhardt RJ, Huang XF, Hsieh-Wilson LC. Angew. Chem. Int. Ed. 2019; 58: 18577
- 17 Characterization Data of Compound 13 Mp 89–91 °C; [α]D 25 –08.1 (c 0.068, CH2Cl2). 1H NMR (400 MHz, DMSO-d 6): δ = 7.75 (d, J = 8.8 Hz, 1 H, H-5), 7.16 (s, 1 H, H-8), 7.11 (d, J = 8.9 Hz, 1 H, H-6), 6.28 (s, 1 H, H-3), 6.02 (s, 1 H, H-1′), 5.16 (s, 1 H, H-3′), 5.04 (s, 2 H, H-2′, H-4′), 4.99 (s, 1 H, H-5′), 3.66 (s, 3 H, OCH3), 2.41 (s, 3 H, 4-CH3), 2.16 (s, 3 H, OAc), 2.10 (s, 3 H, OAc), 2.05 (s, 3 H, OAc). 13C NMR (101 MHz, DMSO-d 6): δ = 169.1 (OAc), 169.0 (C × 2, OAc), 167.3 (COOMe), 159.8 (C-2), 158.1 (C-7), 154.2 (C-9), 153.1 (C-4), 126.7 (C-5), 114.8 (C-10), 113.4 (C-6), 112.2 (C-3), 103.8 (C-8), 95.2 (C-1′), 67.5 (C-5′), 66.8 (C-3′), 66.4(C-4′), 66.0 (C-2′), 52.3 (OCH3), 20.5 (C × 2, OAc), 20.3 (OAc), 18.0 (4-CH3). HRMS (ESI+): m/z calcd for C23H25O12 [M + H]+: 493.1341; found: 493.1346.
- 18 Characterization Data of Compound 14 Mp 119–121 °C; [α]D 25 –111.7 (c 0.081, CH3OH). 1H NMR (400 MHz, DMSO-d 6): δ = 7.73 (d, J = 8.5 Hz, 1 H, H-5), 7.07–7.04 (m, 2 H, H-8, H-6), 6.26 (s, 1 H, H-3), 5.70 (d, J = 4.9 Hz, 1 H, H-1′), 5.57 (d, J = 5.8 Hz, 1 H, 2′-OH), 5.38–5.36 (m, 2 H, 3′-OH, 4′-OH), 4.65 (d, J = 4.3 Hz, 1 H, H-5′), 3.82–3.78 (m, 1 H, H-4′), 3.67–3.63 (m, 4 H, H-3′, COOMe), 3.58–3.53 (m, 1 H, H-2′), 2.40 (s, 3 H, 4-CH3). 13C NMR (101 MHz, DMSO-d6 ): δ = 170.0 (COOMe), 160.0 (C-2), 159.6 (C-7), 154.3 (C-9), 153.2 (C-4), 126.6 (C-5), 114.2 (C-10), 113.3 (C-6), 111.8 (C-3), 103.3 (C-8), 99.0 (C-1′), 71.8 (C-5′), 71.4 (C-3′), 70.7 (C-2′), 70.0 (C-4′), 51.7 (OCH3), 18.1 (4-CH3). HRMS (ESI+): m/z calcd for C17H19O9 [M + H]+: 367.1024; found: 367.1029.
- 19 Characterization Data of 4-Methylumbelliferyl α-l-Idopyranosiduronic Acid (1) Mp 205–207 °C; [α]D 25 –38.3 (c 0.021, CH3OH). 1H NMR (400 MHz, DMSO-d 6): δ = 7.87(s, 1 H, H-8), 7.65 (d, J = 8.8 Hz, 1 H, H-5), 7.34 (dd, J = 8.8, 2.4 Hz, 1 H, H-6), 6.21 (s, 1 H, H-3), 5.51 (d, J = 7.0 Hz, 1 H, 2′-OH), 5.19 (d, J = 4.9 Hz, 1 H, H-1′), 4.96 (d, J = 3.8 Hz, 1 H, 3′-OH), 3.99 (d, J = 6.2 Hz, 1 H, H-3′), 3.25–3.17 (m, 3 H, H-2′, H-4′, H-5′), 2.40 (s, 3 H, 4-CH3). 13C NMR (101 MHz, DMSO-d 6): δ = 172.1 (COOH), 160.8 (C-2), 160.4 (C-7), 154.6 (C-9), 153.4 (C-4), 126.0 (C-5), 113.6 (C × 2, C-10, C-6), 111.3 (C-3), 103.6 (C-8), 97.3 (C-1′), 74.4 (C-5′), 73.1 (C-3′), 72.5 (C-4′), 71.1 (C-2′), 18.1 (4-CH3). HRMS (ESI+): m/z calcd for C16H17O9 [M + H]+: 353.0867; found: 353.0868.