Abstract
The relative rates of enzyme-catalyzed esterification of the enantiomers of 2-octanol with various acids were determined for several commercial lipases. Interesterifications and hydrolyses of racemic 2-octanol esters catalyzed by these enzymes were also examined. Novo'sMucor miehei lipase exhibited considerable enantioselectivity and was therefore employed to prepare 8-methyl-2-decanols with high configurational purity at the carbinol carbon. Esters of these alcohols had been previously identified as sexually attractive to several rootworm (Diabrotica) species, and the stereochemistry of those esters had been shown to be critical to the attraction. The enzymatic resolution provides a convenient method to obtain such esters in a desired state of configurational purity.
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References
Borgstrom, B., andBrockman, H.L. 1984. Lipases. Elsevier, New York.
Brand, J.M., Young, J. Chr., andSilverstein, R.M. 1979. Insect pheromones: A critical review of recent advances in their chemistry, biology, and application.Fortschr. Chem. Org. Naturst. 37:91–104.
Brockerhoff, H., andJensen, R.G. 1974. Lipolytic Enzymes. Academic Press, New York.
Cambou, B., andKlibanov, A.M. 1984a. Preparative production of optically active esters and alcohols using esterase-catalyzed stereospecific transesterification in organic media.J. Am. Chem. Soc. 106:2687–2692.
Cambou, B., andKlibanov, A.M. 1984b. Lipase-catalyzed production of optically active acids via asymmetric hydrolysis of esters.Appl. Biochem. Biotech. 9:255–260.
Doolittle, R.E., andHeath, R.R. 1984. (S)-Tetrahydro-5-oxo-2-furancarboxylic acid: A chiral derivatizing reagent for asymmetric alcohols.J. Org. Chem. 49:5041–5050.
Gramatica, P., Manitto, P., andPoli, L. 1985. Chiral synthetic intermediatesvia asymmctric hydrogenation of α-methyl-α, β-unsaturated aldehydes by Baker's yeast.J. Org. Chem. 50:4625–4628.
Guss, P.L., Sonnet, P.E., Carney, R.L., Tumlinson, J.H., andWilkin, P.J. 1985. Response of the northern corn rootworm,Diabrotica barberi Smith & Lawrence, to stereoisomers of 8-methyl-2-decyl propanoate.J. Chem. Ecol. 11:21–26 (and earlier references cited therein).
Hamaguchi, S., Asada, M., Hasagawa, J., andWatanabe, K. 1984. Biological resolution of racemic 2-oxazolidones. Part II. Assymmetric hydrolysis of racemic 2-oxazolidone esters with lipases.Agric. Biol. Chem. 48:2331–2337.
Hamaguchi, S., Asada, M., Hasagawa, J., andWatanabe, K. 1985. Stereospecific hydrolysis of 2-oxazolidone esters and separation of products with an immobilized lipase column.Agric. Biol. Chem. 49:1661–1667.
Ladner, W.E., andWhitesides, G.M. 1984. Lipase-catalyzed hydrolysis as a route to esters of chiral epoxy alcohols.J. Am. Chem. Soc. 106:7250–7251.
Langrand, G., Secchi, M., Buono, G., Baratti, J., andTriantaphylides, C. 1985. Lipasecatalyzed ester formation in organic solvents: An easy preparative resolution of α-substituted cyclohexanols.Tetrahedron Lett. 26:1857–1860.
Laumen, K., andSchneider, M. 1984. Enzymatic hydrolysis of prochiralcis-1,4-diacyl-2-cyclopentenediols: Preparation of (1S,4R)- and (1R,4S)-4-hydroxy-2-cyclopentenyl derivatives, versatile building blocks for cyclopentanoid natural products.Tetrahedron Lett. 25:5875–5878.
Lavayre, J., Verrier, J., andBaratti, J. 1982. Stereospecific hydrolysis by soluble and immobilized lipases.Biotechnol. Bioeng. 24:2175–2187.
Martin, V.S., Woodard, S.S., Katsuki, T., Yamada, Y., Ikeda, M., andSharpless, K.B. 1981. Kinetic resolution of racemic alcohols by enantioselective epoxidation. A route to substances of absolute enantiomeric purity.J. Am. Chem. Soc. 103:6237–6240.
Mori, K. 1981. A simple synthesis of (S)-(+)-sulcatol, the pheromone ofGnathotrichus retusus, employing baker's yeast for asymmetric reduction.Tetrahedron 37:1341–1342.
Mori, K., andAkao, H. 1980. Synthesis of optically active alkynyl alcohols and α-hydroxy esters by microbial asymmetric hydrolysis of the corresponding acetates.Tetrahedron 36:91–96.
Mori, K., andIwasawa, H. 1980. Preparation of the both enantiomers ofthreo-2-amino-3-methylhexanoic acid by enzymatic resolution and their conversion to optically active forms of threo-4-methylheptan-3-ol, a pheromone component of the smaller European elm bark beetle.Tetrahedron 36:2209–2213.
Mori, K., Mori, H., andSugai, T. 1985. Biochemical preparations of both the enantiomers of methyl 3-hydroxypentanoate and their conversion to the enantiomers of 4-hexanolide, the pheromone ofTrogoderma glabrum.Tetrahedron 41:919–925.
Pirkle, W.H., andHauske, J.R. 1977. Trichlorosilane-induced cleavage. A mild method for retrieving carbinols from carbamates.J. Org. Chem. 42:2781–2782.
Satoru, K., Sonomoto, K., Tanaka, A., andFukui, S. 1985. Stereoselective esterification ofdl-menthol by polyurethane-entrapped lipases in organic solvent.J. Biotechnol. 2:47–57.
Sonnet, P.E., Carney, R.L., andHenrick, C. 1985. Synthesis of stereoisomers of 8-methyl-2-decanol and esters attractive to severalDiabrotica sp.J. Chem. Ecol. 11:1371–1387.
Sonnet, P.E., Pfeffer, P.E., andWise, W.B. 1986. Evaluation of some approaches to liquified tallow: Stereochemical consequences of interesterification.J. Am. Oil Chem. Soc. 63(12):1560–1564.
Sugai, T., andMori, K. 1984. Synthesis of both the enantiomers of 4-dodecanolide, a defensive secretion of rove beetles.Agric. Biol. Chem. 48:2497–2500.
Wang, Y.-F., Chen, C.-S., Girdaukas, G., andSih, C.J. 1984. Bifunctional chiral synthons via biochemical methods. 3. Optical purity enhancement in enzymic asymmetric catalysis.J. Am. Chem. Soc. 106:3695–3696.
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Sonnet, P.E., Baillargeon, M.W. Kinetic resolution of secondary alcohols with commercial lipases. J Chem Ecol 13, 1279–1292 (1987). https://doi.org/10.1007/BF01020554
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DOI: https://doi.org/10.1007/BF01020554