Search

A method is described for the synthesis of (±)-2,3-epoxy propyl esters from glycerol, involving reaction of epichlorohydrin with sodium or potassium salts of carboxylic acids in the presence of TBAB as catalyst, with moderate to excellent yields. Kinetic resolution of glycidyl butyrate by lipase of Thermomyces lanuginosa has been achieved with remarkable enantiomeric excess (ee >99%) using 1,4-dioxane as a co-solvent in pure buffer solution (30 and 50 °C, pH = 7.0).

This paper addresses the effects of the concentration of lipases, temperature and solvent on the enzymatic acetylation of primary amines. (±)-Heptan-2-amine 1, (±)-4-phenylbutan-2-amine 2, (±)-1,2,3,4-tetrahydronaphthalen-1-amine 3 and (±)-2-methylcyclohexan-1-amine 4 were acetylated using 11 lipases to obtain amides under orbital shaking and microwave radiation. Under microwave radiation the same amines were acetylated only using the CALB. (±)-Heptan-2-amine 1 was subjected to kinetic resolution, under orbital shaking for 7 h employing CALB and ethyl acetate as acylating agent, and converted into (R)-N- (heptan-2-yl)acetamide 5 (c = 42%, 88% ee

Aromatic and aliphatic nitriles are common intermediates in the industrial production of polyamides, pharmaceuticals, agrochemicals, dyes, pigments, and fine chemicals 1 . Moreover, in organic synthesis the nitrile group serves as an important starting material for various transformations into other functional groups, such as amines, aldehydes, ketones, heterocycles 2 . In this work a new way to synthesize benzonitriles is reported.

As lipases têm um papel importante no desenvolvimento da biotecnologia e são empregadas na química orgânica como biocatalisadores com alta regio- quimio- e enantiosseletividade. Além de permitir sínteses mais sustentáveis e que estão em concordância com os princípios da Química Verde. A resolução enzimática de aminas racêmicas tem se mostrado uma maneira eficiente de obter aminas enantiomericamente puras, que podem ser empregadas na síntese assimétrica de fármacos e agroquímicos. Neste trabalho a resolução enzimática de 4 aminas primárias sendo elas 2-amino-heptano 1, 2-metil-cicloexil amina 3, 1-metil-3-fenilpropilamina 2, 1,2,3,4-tetra-hidro-1-naftilamina 4, foram estudadas obtendo-se resultados relevantes. Para a 2-amino-heptano 1 resultados semelhantes aos da literatura foram obtidos com uma redução de 2,4 vezes no tempo reacional quando a resolução cinética foi em hexano na presença de CAL-B e acetato de etila como acilante obteve-se uma conversão na (R)-N-(1-metil-hexil)acetamida 4 de 42% e um excesso enantiomérico de 88% (tempo = 7h). Observaram-se também os efeitos da concentração de lipase no meio reacional, da temperatura e de diferentes solventes frente a 11 lipases. Os primeiros estudos de resolução cinética enzimática com a 2-metilcicloexil-amina 3 são apresentados neste trabalho com conversões de até 98% porém sem excesso enantiomérico. Uma outra característica das lipases é a capacidade de catalisar reações diferentes da sua função natural (promiscuidade), o que permite que elas catalisem reações de adição de Michael, além de suas reações normais que são a hidrólise e esterificação. A adição de Michael catalisada por lipases entre as 4 aminas primárias já citadas e acrilonitrila foi estudada com e sem a influência da irradiação micro-ondas, demonstrando a maior estabilidade de lipases imobilizadas sob irradiação micro-ondas. Os adutos de Michael obtidos (3-[(1-metil-hexil)amino]propanonitrila 9, 3-[(1-metil-3-fenilpropil) amino]propanonitrila 10, 3-[(2-metil cicloexil)amino]propanonitrila 11 e 3-(1,2,3,4-tetra-hidronaftaleno-1-amino)propanonitrila 12) foram sintetizados pela primeira vez com a metodologia onde foi utilizada a água, acrilonitrila e irradiação micro-ondas e os adutos 9, 10 e 11 não são descritos na literatura. Outro viés do trabalho foi a clonagem e expressão da álcool desidrogenase de Bacillus subtilis que foi clonada, expressa e purificada com sucesso. O interesse em tal enzima deve-se a resultados obtidos na literatura onde a utilização de células íntegras de B. subtilis apresentou a redução de cetonas a álcoois com alta enantiosseletividade. Lipases present an important role in the development of biotechnology and are employed as biocatalysts in organic chemistry with high regio-, quimioand enantioselectivity. Besides allowing more sustainable syntheses that are consistent with the principles of Green Chemistry. The enzymatic resolution of amines has been shown to be an efficient way to obtain enantiomerically pure amines, which can be used in asymmetric synthesis of pharmaceuticals and agrochemicals. In this work the enzymatic resolution of 4 primary amines them being 2-amino-heptane textbf 1, 2-methyl-cyclohexyl amine 3, 1-methyl-3-phenylpropylamine 2 1.2 ,3,4-tetrahydro-1-naphthylamine 4 were studied by obtaining relevant results. For the 2-amino-heptane 1 promoted results similar to the literature and were obtained with a 2.4 times reduction of the reactional time when the kinetic resolution was in hexane in the presence of CAL-B and ethyl acetate as acylating obtained a conversion in (R)-N-(1-methyl-cyclohexyl) acetamide 4 by 42 % and an enantiomeric excess of 88 % (time = 7h). We studied the effects of the concentration of lipase in the reaction, temperature and solvent using 11 different lipases. The first studies of enzymatic kinetic resolution with 2-methyl-cyclohexyl- amine 3 are presented in this work with conversions up to 98% but without enantiomeric excess. The ability of lipases to catalyze reactions with different natural function (promiscuity) is an important property, which allows them to catalyze Michael addition reactions beyond their normal reactions, the hydrolysis and esterification. The Michael addition catalyzed by lipases between the four aforementioned primary amines and acrylonitrile was studied with and without the influence of microwave irradiation, demonstrating the greater stability of immobilized lipases under microwave irradiation. The Michael adducts obtained (3 - [(1-methylhexyl) amino] propanonitrile 9, 3 - [(1-methyl-3-phenylpropyl) amino] propanonitrile 10, 3 - [(2 - methyl cyclohexyl) amino] propanonitrile 11 and 3 - (1,2,3,4-tetrahydronaphthalene-1-amino) propanonitrile 12) were first synthesized with the method where water is used, acrylonitrile and microwave radiation, the adducts 9,10 and 11 are not described in the literature. Another investigation of this study was the cloning and expression of alcohol desidrogrenase of Bacillus subtilis which has been cloned, expressed and purified successfully. Interest in the enzyme due to results in the literature where the use of whole cells of B. subtilis showed the reduction of ketones with high enantioselectivity.

Presently glycerol is considered a co-product of biodiesel industry. As the biodiesel production is exponentially increasing, glycerol generated from the transesterification of vegetable oils and fats is also being produced on a large scale, and turned out to be essential seeking for novel alternatives to the consumption of the extra volume, in crude and/or as derivatives high added value. This review mainly deals with chemical and enzymatic transformations of glycerol to obtain chiral building blocks for synthesis of pharmaceuticals and natural products.