Enzyme-catalyzed Regioselective Synthesis of Novel Raffinose Vinyl Esters

Abstract

Abstract: Sugar esters have recently received increased attention from the viewpoint of renewable resources.Specifically vinyl esters from carbohydrates by enzyme-catalyzed regioselective transformations offer a new family of functional water-soluble monomers for preparation of sugar-based polymers.Here we reported enzyme-catalyzed regioselective synthesis of novel polymerizable raffinose vinyl ester.Transesterification of raffinose with divinyl succinate, divinyl adipate and divinyl sebacate in anhydrous pyridine at 50℃ for₆d was catalyzed by an alkaline protease from Bacillus subtilis.Three raffinose vinyl esters with different acyl donor chain lengths were regioselectively synthesized at 55%, 48% and 30% yields, respectively.Characterization of the products by ¹HNMR, ¹³CNMR, and ¹H-¹Hcorrelation spectroscopy and ¹H-¹³C heteronuclear multiple quantum coherence NMR revealed that the ester was substituted at C-1 position of β-fructofuranose moiety in raffinose.Reaction conditions for the esterification were investigated.Activities of seven commercial enzymes from different sources catalyzing synthesis of raffinose ester were compared.Lipase from porcine pancreas(PPL) and alkaline protease from Bacillus subtilis had high activities.We also studied the effect of temperature and incubation time on raffinose esters synthesis catalyzed by alkaline protease from Bacillus subtilis and found the optimal temperature and reaction time were 50℃ and 6d respectively.

Key words: Raffinose, Vinyl ester, Enzyme catalyzed synthesis, Transesterification

CLC Number:

O626

TrendMD:

WU Qi, Lü De-Shui, CHEN Zhi-Chun, YU Guo-Hua, LIN Xian-Fu . Enzyme-catalyzed Regioselective Synthesis of Novel Raffinose Vinyl Esters[J]. Chem. J. Chinese Universities, 2003, 24(10): 1806.

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Enzyme-catalyzed Regioselective Synthesis of Novel Raffinose Vinyl Esters

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