Lipase catalyzed synthesis

Lipase-catalyzed synthesis of polyesters from cyclic anhydrides and oxi-ranes was reported. The polymerization took place by PPL catalyst and the molecular weight reached 1 x 10" under the selected reaction conditions. During the polymerizahon, the enzymatically formed acid group from the anhydride may open the oxirane ring to give a glycol, which is then reacted with the anhydride or acid by lipase catalysis, yielding the polyesters. 

Takamoto T, Uyama H, Kobayashi S (2001) Lipase-catalyzed synthesis of aliphatic polyesters in supercritical carbon dioxide. e-Polymers no.004... 

Nagao, A. and Kite, M. (1990) Lipase-catalyzed synthesis of fatty acid esters useful in the food industry. Biocatalysis, 3, 295-305. 

At the end of the previous chapter, we discussed the medium dependence of the lipase-catalyzed synthesis of nifedipines, dihydropyridines with an aromatic substituent in the 4-position and often asymmetric ester derivatives in the 3- and 5-positions, which are active as calcium antagonists in cardiovascular therapy. At the Amano Company in Nagoya, Japan, lipase-catalyzed hydrolyses of methylene-oxypropionyl or -pivaloyl diesters with Amano PS (Pseudomonas sp.) lipase were found to yield varying enantiomeric excesses depending on the solvent in cyclohexane the different esters yielded half-esters with 88.8-91.4% e.e. (R)-specificity for a triple mutant ( FVL ) of Amano PS lipase, whereas the same transformation with the same enzyme in diisopropyl ether (DIPE) yielded between 68.1 and > 99% e.e. of the (S)-product (Chapter 12, Figure 12.10) (Hirose, 1992,1995). 

Tsuji T, Onishi T et al (1999) Lipase-catalyzed synthesis of a tri-substituted cyclopropyl chiral synthon a practical method for preparation of chiral l-alkoxycarbonyl-2-oxo-3-oxabicyclo[3.1.0]hexane. Tetrahedron Asymmetry 10 3819-2825... 

Kobayashi, S. (2009). Recent developments in lipase-catalyzed synthesis of polyesters. Macromol. Rapid Commun., 30, 237-266. 

Lipase-catalyzed synthesis of chiral 1,4-dihydropyridines and barbiturates as drugs 91YGK1127. 

Soumanou, M.M., Bornscheuer, U.T., Schmid, U., Schmid, R.D. 1999. Crucial role of support and water activity on the lipase-catalyzed synthesis of structure triglycerides. Biocatal. Biotransform. 16, 443 159. 

The adequacy of the predicted model here was examined by additional independent experiments at the suggested optimum synthesis conditions. The predicted value was 99.4% molar conversion and the actual experimental value was 97.9%. A chi-square test (p-value = 0.96, degrees of freedom = 5) indicated that observed values were significantly the same as the predicted values and the generated model adequately predicted the percent molar conversion (Ott, 1988). Thus, the optimization of lipase-catalyzed synthesis for biodiesel (canola oil methyl ester) by Novozym 435 was successfully developed by CCRD and RSM. 

Soumanou, M. M., and Bornscheuer, U. T. 2003. Improvement in lipase-catalyzed synthesis of fatty acid methyl esters from sunflower oil. Enzyme and Microb. Technol, 33, 97-103. 

Fig. 8.38 Lipase-catalyzed synthesis of fatty acid esters.

Matos JR, Blair WJ, Wong CH (1987) Lipase catalyzed synthesis of peptides preparation of a penicillin G precursor and other. Biotechnol Lett 9 233-236... 

Butsat, S. Siriamompun, S. 2010. Antioxidant capacities and phenolic compounds of the husk, bran and endosperm of Thai rice. Food Chem. 119 606 613. Chigorimbo-Murefu, N.T.L. Riva, S. Burton, S.G. 2009. Lipase-catalyzed synthesis of esters of ferulic acid with natural compounds and evaluation of their antioxidant properties. J. Molec. Cat. B Enzym. 56 277-282. 

Effect of Acyl Donors. TTie synthesis of glucose fatty acid esters was investigated with continuous by-product removal in a stirred-tank membrane reactor by azeotropic distillation using EMK containing 20% hexane as reaction solvent and different fatty acids as acyl donors. From previous studies on the lipase-catalyzed synthesis of glucose esters in a solid-phase system (17,19,22,23), it was already known that the fatty acid chainlength had a considerable influence on product formation. This was due... 

Oguntimein, G.B., H. Erdmann, and R.D. Schmid, Lipase-Catalyzed Synthesis of Sugar Ester in Organic Solvents, Biotechnol. Lett. 75.-175-180 (1993). 

Yamane, T. Lipase-catalyzed synthesis of structured triacylglycerols containing polyunsaturated fatty acids monitoring the reaction and increasing the yield. In Enzymes in Lipid Modification Bornscheuer, U.T., Ed. Wiley-VCH Weinheim, Germany, 2000 148-169. 

Hayes, D.G. Lipase-catalyzed synthesis of poly-hydric alcohol-poly(ricinoleic acid) ester star polymers. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 2005, 46 (1), 276-277. 

Scheme 2 Lipase-catalyzed synthesis of succinated guar.

The choice of immobilization matrix material must be made carefully because its polarity, or aquaphilicity (water-adsorption capability), and the chemistry of its charged surface groups can affect the observed enantioselectivity and the occurrence of side reactions, particularly hydrolysis and isomerization (e.g., of mono-and diglycerides during lipase-catalyzed synthesis of structured triglycerides). In the situations alluded to above, it may be worthwhile to screen the various immobilization matrices. 

Bjorkling, R, Frykman, H., Godtfredsen, S. E., and Kirk, O., Lipase catalyzed synthesis of peroxycarboxyhc acids and lipase mediated oxidations. Tetrahedron, 48, 4587-4592, 1992. 

Selmi, B., Gontier, E., Ergan, R, Barbotin, J. N., and Thomas, D., Lipase-catalyzed synthesis of tricapryhn in a medium solely composed of substrates. Water production and elimination. Enzyme Microbiol. TechnoL, 20, 322-325, 1997. 

In 1999, Orsat et al. [107, 108] discussed the lipase-catalyzed synthesis of ( )-retinyl acetate (185), an intermediate used in the synthesis of retinol (vitamin A) (186) (Scheme 6.48). Pumping a solution of the alcohol 187, in vinyl acetate (147) (10% w/v), through a packed bed containing 5.0 g of biocatalyst 188, the authors were... 

Okumara and co-workers [10] were the first to attempt the lipase-catalyzed synthesis of oligoesters from reactions between diols (AA) and dicarboxylic acids (BB). They showed that trimer , pentamer , and heptamer consisting of AA-BB-AA, AA-BB-AA-BB-AA, and AA-BB-AA-BB-AA-BB-AA, respectively, were formed. Klibanov et al. [121] used the stereoselectivity of lipases to prepare enantioen-riched oligoesters. The reactions were conducted using racemic diester and an achiral diol or, conversely, a racemic diol and an achiral diester as monomers (see also Chapter 11). 

Lipase-catalyzed synthesis of poly(l,4-butyl sebacate) from reactions of 1,4-butanediol and sebacic acid or activated derivatives of sebacic acid were studied by Linko et al. [51]. Reactions between 1,4-butanediol with sebacic acid,... 

The phase separation of reactants hindered attempts to carry out lipase-catalyzed synthesis of poly(butylene succinate) (PBS) from succinic acid and 1,4-butanediol via dehydration. Therefore, in order to obtain a monophasic reaction mixture, dimethyl succinate was used in place of succinic acid. [49] The reaction mixture remained monophasic during the reaction course, and after 21 h at 95 °C PBS with M of 38000 was obtained. 

Scheme 4.6 Porcine pancreatic lipase-catalyzed synthesis of enantio-enriched polyester with epoxy groups in the main chain.

Scheme 4.27 Pseudomonas fluorescens lipase-catalyzed synthesis of poly (MBC-co-TMC).

Lipase-catalyzed synthesis of polyesters came to the focus after two major breakthroughs in 1984, novel lipase-catalyzed polycondensation to give oli-goesters in 1993, discovery of the catalysis for ring-opening polymerization of lactones. 

Olsson, A., Lindstrom, M., and Iversen, T. (2007) Lipase-catalyzed synthesis of an epoxy-functionalized polyester from the suberin monomer cis-9,10-epoxy-18-hydroxyodadecanoic acid. Biomacromolecules, 8 (2), 757-760. 

Ebata, H., Toshima, K., and Matsumura, S. (2007) Lipase-catalyzed synthesis and curing of high-molecular-weight polyricinoleate. Macromol. Biosci., 7 (6), 798-803. 

Uyama, H., Inaka, K., and Kobayashi, S. (2000) Lipase-catalyzed synthesis of aliphatic polyesters by polycondensation of dicarboxylic acids and glycols in solvent-free system. Polym. J., 32 (5), 440-443. 

J. (1995) Lipase-catalyzed synthesis of poly(1,4-butyl sebacate) from sebacic acid or its derivatives with 1,4-butanediol./. Biotechnol., 40 (2), 133-138. 

Jiang, Y., Liu, C., and Gross, R.A. (2008) Lipase-catalyzed synthesis of aliphatic poly(carbonate-co-esters). Macromolecules, 41 (13), 4671-4680. 

Li, G., Yao, D., and Zong, M. (2008) Lipase-catalyzed synthesis of biodegradable copolymer containing malic acid units in solvent-free system. Eur. Polym.J., 44 (4), 1123-1129. 

So, ).E Kang, S.H., and Kim, B.G. (1998) Lipase-catalyzed synthesis of peptides containing D-amino acid. Enzyme Microb. Technol, 23 (3-4), 211-215. 

Lipase-catalyzed Synthesis and Polymerization of Optically Pure Monomers... 

Scheme 11.1 Lipase-catalyzed synthesis of poly(L-lactide) (10).

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