Synthesis of an acryloyl‐type polymer pending D‐glucose analog of N‐acetylmuramyl‐L‐alanyl‐D‐isoglutamine

Abstract

Poly[l -(3-0-[ 1-( 1-carboxyethylaminocarbonyl)ethyl]-6-O-~-glucopyranosyIcarbonyl]ethylene] (3 b) was synthesized as the lipophilic and polymeric model of 4-{N-[2-(2-acetylamino-2-deoxy-3-O-~-glucopyranosyl)propionyl]-~-alanylamino]glutamic acid (1) to the minimum required structure for the immunoadjuvant activity of bacterial cell wall. N-[2-(6-O-acryloyl-l,2-O-isopropylidene-a-~-3-O-g~ucofuranosy~)propiony~]-~-a~a~ne benzyl ester (6) was prepared as a key monomer in the synthesis. The homopolymerization of this monomer was carried out in benzene at 50°C using 2,2'-azoisobutyronitrile as radical initiator to give polymer 7. From the results of copolymerization with styrene, the values of Q and e for the acryloyl type monomer 6 were estimated to be 2,O and O,ll, respectively. The removal of isopropylidene and benzyl protecting groups from homopolymer 7 was carried out by acidic treatment with trifluoroacetic acid/water (vol. ratio 6: 1) and by catalytic hydrogenolysis with palladium carbon in acetone, respectively, to afford the homopolymer 3 b. *) Systematic name: 4-[N-[2-(~-acety~amino-2-deoxy-3-~-~-g~ucopyranosy~)propiony~]-~-a~an-y1amino)glutamic acid.

Nitroxide-controlled free radical polymerization of a sugar-carrying acryloyl monomer

“…2 : 5,Fig. 1 b) This synthesis was made by a slight modification of the method proposed by Ouchi et al 15) . To a cold solution of 1,2 : 5,6-di-O-isopropylidene-D-glucofuranose (26 g, 0.1 mmol) in dry acetone (100 mL) with triethylamine (40 mL, 0.3 mmol), acryloyl chloride (25 mL, 0.3 mmol) was added dropwise at 0 8C.…”

Michael-type Addition as a Convenient Method for Regioselective N-Alkylation of Ambident Uracils

“…The addition of 5-fluorouracil to 1,2:5,6-di-O-isopropylidene-3-O-acryloyl-a-D-glucofuranose was applied in the synthesis of N1-modified nucleosides containing a propionyl linker. 73,74 The introduction of the linker was performed at various stages (Scheme 13). Apart from the Michael-type addition, the target compound was synthesised by way of an alternative route, namely condensation of 3-(uracil-1-yl)propionic acid with the sugar moiety in the presence of N,N¢-dicyclohexylcarbodiimide.…”

Do Photolyases Need To Provide Considerable Activation Energy for the Splitting of Cyclobutane Pyrimidine Dimer Radical Anions?

“…Synthesis of model compounds 1–3 : The cis–syn thymine dimer dicarboxylic acid was prepared from thymine,10a and the ethyl ester of 1‐(2‐carboxyethyl)uracil ( 5 )17 from uracil according to methods in the literature. The acetone/water solution of 5 was placed in a Pyrex photoreactor ( λ >290 nm) accompanying to bubble with highly pure N 2 and irradiated by a 300 W high‐pressure Hg lamp.…”

“…Ethyl‐ cis ‐[4 a ]‐ cisoid ‐[4 a ,4 b ]‐ cis ‐[4 b ]‐dodecahydro‐2,4,5,7‐tetraoxocyclobuta [1,2‐ d :4,3‐ d ]‐dipyrimidine‐1,8‐dipropionate (6) : Compound 5 17 (2.00 g, 9.4 mmol) was dissolved in acetone/H 2 O (200 mL, 7:3) and the solution was degassed for 15 min in an ultrasonic bath. The solution was irradiated for 6 h with a 300 W high‐pressure Hg lamp in a Pyrex photochemical reactor.…”