Convenient syntheses of cytidine 5'-triphosphate, guanosine 5'-triphosphate, and uridine 5'-triphosphate and their use in the preparation of UDP-glucose, UDP-glucuronic acid, and GDP-mannose

Abstract

data, mp, ^, and e for 6 except for 6e were reported previously.11 -(tert-Butylamino)-2,4-dinitronaphthalene (6e): mp 115-115.5 °C; XmaJ 408 nm (e 11600 [MeOH]); NMR (DMSO-d6) 1.33 [s, 9 H, C(CH3)3], 7.97 (br s, 1 , NH, overlapped with 6,7), 8.03 (qui, 2 , H6", partially overlapped with NH), 8.70 (m, 2 , H5,8, overlapped with each other), 9.03 (s, 1 , H3), in which the suffix on hydrogen represents the positional number of a naphthalene moiety.Determination of Products. The typical procedure for determination of the reaction products is described for the reaction of 6d with methylamine. The 10-mL DMSO solution containing 5 mmol (0.137 g) of 6d and 3 equiv of methylamine (40% solution) was stirred for the prescribed time at the prescribed temperature, and then the mixture was poured into 200 mL of water, acidified with the equiv of HC1 based on the methylamine added, extracted with 200 mL of benzene three times, and dried over anhydrous MgS04. After the mixture was filtered, the benzene layer was subjected to HPLC (Shimazu LC-6A, silica gel, hexane-2-propanol (20:1 v/v).

A chemical synthesis of UDP-LacNAc and its regioisomer for finding ‘oligosaccharide transferases’

“…Condensation of 10 with UMP-imidazolate (11), which was prepared by Whitesides's procedure [11], in dry pyridine at room temperature and subsequent de-O-acetylation [12] in MeOH/H 2 O/Et 3 N (7/3/1) for 24 h at room temperature afforded 3-monoacetylated UDPLacNAc as a main product. For removing the acetyl group at hindered position, de-O-acetylation was carried out in MeOH/H 2 O/Et 3 N (7/3/3) for 24 h at 35 • C and followed by purification by anion-exchange column HPLC (Hamilton RCX-10, eluent: 0.3 M HCOONH 4 ) and column chromatography on Sephadex G-10 to give the UDP-LacNAc (12) as an ammonium salt in 77 % yield (Scheme 2).…”

“…Reductive removal of the benzyl groups in 20 gave 21 in 97 % yield. Condensation of 21 with UMPimidazolate (11) in dehydrated pyridine at room temperature and subsequent de-O-acetylation in MeOH/H 2 O/Et 3 N (7/3/3) for 24 h at 35 • C produced the Galβ(1→3)GlcNAc-UDP (22) as an ammonium salt in 77 % yield after purification in the same way as described for 12 (Scheme 4). The significant signals in the 1 H-NMR spectrum of 22 were the one-proton doublet of doublets at δ 5.35 ppm (J 1,2 = 3.4 Hz, 3 J 1,P = 7.6 Hz, H-1 of GlcNAc), one-proton doublet at δ 5.82 ppm (J 1,2 = 5.5 Hz, H-1 of Rib), one-proton doublet at δ 5.81 ppm (J 5,6 = 8.2 Hz, H-5 of Ura) and one-proton doublet at δ 7.81 ppm (J 5,6 = 8.2 Hz, H-6 of Ura).…”

“…The filtrate was concentrated and the residue was lyophilized with 1,4-dioxane to give compound 10 (268 mg, 96 %) as a colorless powder. 5, 20.6, 20.7, 20.8, 21.2, 22.6, 62.3, 63.2, 68.6, 70.5, 70.7, 71.7, 72.5, 72.8, 77.3, 102, 128.1, 128.5, 170.9, 171.3, 171.8, 171.9, 172.0, 172.4, 173; 31 (12) Uridine 5 -monophosphoimidazolate (11) was prepared by Whitesides's procedure. [11] To a solution of Uridine 5 -monophosphate disodium salt (21.2 mg, 57.6 μmol) in H 2 O was added Amberlite IR-120 (H + form).…”

“…5, 20.6, 20.7, 20.8, 21.2, 22.6, 62.3, 63.2, 68.6, 70.5, 70.7, 71.7, 72.5, 72.8, 77.3, 102, 128.1, 128.5, 170.9, 171.3, 171.8, 171.9, 172.0, 172.4, 173; 31 (12) Uridine 5 -monophosphoimidazolate (11) was prepared by Whitesides's procedure. [11] To a solution of Uridine 5 -monophosphate disodium salt (21.2 mg, 57.6 μmol) in H 2 O was added Amberlite IR-120 (H + form). After stirring for 30 min, the insoluble materials was filterd, and trioctylamine was added (25 μl, 58 μmol) to neutralize.…”

Efficient Synthesis of Nucleoside Diphosphate Glycopyranoses

“…[4,5] However, this reaction normally takes days, and the chemical yields are often low (5-25 %). Attempts to improve the reaction yields by using 1H-tetrazole as activator [6][7][8][9] are often not successful and have failed also in our hands. Instead of the morpholidates, also imidazolides have been used in the past but without improving the yields markedly.…”