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Approaches to 2-Methyl-1-Alkanols of High Enantiomeric Purities Via Enzyme Mediated Reactions

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Microbial Reagents in Organic Synthesis

Part of the book series: NATO ASI Series ((ASIC,volume 381))

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Abstract

Methods for the preparation of chiral nonracemic 2-methylalkanols are reviewed with emphasis on microbial processes. Special attention is devoted to two reactions: 1. (S)-2-methylalkanols were obtained from the bakers’ yeast reduction of 2-methyl-3-(2-thienyl)propenals to the corresponding (S)-2-methylthienylpropanols followed by Raney nickel reduction and 2. Racemic 2-methylalkanoic acids were resolved via esterification using lipase from Candida cylindracea.

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References

  • Anderbrant, O, Löfqvist, J, Högberg, H.-E., Hedenström, E., Bengtsson, M. and Magnusson, G. (1992) “Field Response of the Pine Sawfly Neodiprion sertifer to all eight Diprionyl Acetate Stereoisomers”, Entomol. Exp. Appl., 62, 169–181.

    Article  CAS  Google Scholar 

  • Berglund, P., Holmquist, M., Hedenström, E., Hult, K. and Högberg, H.-E. (unpubl.) “The variation in Enantiomeric Ratio as a Function of the Chain Length of the Alcohol Component in the Enzyme Catalyzed Resolution of 2-Methylalkanoic Acids. Preparation of Optically Pure (R)- and (S)-Methyldecanoic Acid”.

    Google Scholar 

  • Crout, D.H.G. and Christen, M. (1989) “Biotransformations in organic Synthesis” in Scheffold, R. ed., Modern Synthetic Methods, vol 5, pp 3–113, Springer Verlag, Berlin.

    Google Scholar 

  • Csuk, R. and Glänzer, B. I. (1990) “Bakers’ Yeast Mediated Transformations in Organic Chemistry.” Chem. Rev., 91,49.

    Article  Google Scholar 

  • Delinck, D. L. and Margolin, A.L. (1991) “Synthesis of chiral building blocks for selective adenosine receptor agents. Lipase-catalyzed reaolution of 2-benzylpropanol and 2-benzylpropionic acid.” Tetrahedron Lett., 31, 6797–6798.

    Article  Google Scholar 

  • Engel, K.-H. (1991) “Lipase-Catalyzed Ensantioselective Esterification of 2-Methylalkanoic Acids.” Tetrahedron Asym., 2, 165–168.

    Article  CAS  Google Scholar 

  • Evans, D. A., Dow, R. L., Shih, T. L., Takacs, J. M. and Zahler, R. (1990b) “Total Synthesis of the Polyether Antibiotic Ionomycin.” J. Am. Chem. Soc., 112, 5290–5313.

    Article  CAS  Google Scholar 

  • Evans, D. A., Ennis, M. D. and Mathre, D. J. (1982) “Asymmetric Alkylation Reactions of Chiral Imide enolates. A Practical Approach to the Enantioselective Synthesis of a-Substituted Carboxylic Acid Derivatives.” J. Am. Chem. Soc. 104, 1737–1739.

    Article  CAS  Google Scholar 

  • Evans, D. A., Rieger, D. L., Jones, T. K. and Kaldor, S. W. (1990a) “Assignment of Stereochemistry in the Oligomycin/Rutamycin/Cytovaricin Family of antibiotics. Asymmetric Synthesis of th Rutamycin Spiroketal synthon.” J. Org. Chem., 55, 6260–6268.

    Article  CAS  Google Scholar 

  • Evans, D. A. and Takacs, J. M. (1980) “Enantioselective alkylation of chiral enolates.” Tetrahedron Lett., 21, 4233–4236.

    Article  CAS  Google Scholar 

  • Ferraboschi, P., Grisenti, P., Casati, R., Fiecchi, A. and Santaniello, E. (1987a) “Biohydrogenation of Unsaturated Compounds by Saccharomyces cerivisiae. Part 1. Stereochemical Aspects of the Reaction and Preparation of Useful Bifunctional Chiral Synthons.” J. Chem. Soc. Perkin Trans. I 1743–1748.

    Google Scholar 

  • Ferraboschi, P., Grisenti, P., Manzocchi, A. and Santaniello, E. (1987b) “New Chemoenzymatic Synthesis of (R)- and (S)- 4-(phenylsolfonyl)-2-methyl-1-butanol: a Chiral C5 Isoprenoid Synthon.” J. Org. Chem., 55, 6214–6216.

    Article  Google Scholar 

  • Fischer, F. G. (1940) “Die Benutzung biochemischer Oxydation und Reduktion für präparative Zwecke.” Angew. Chemie, 53, 461–471.

    Article  CAS  Google Scholar 

  • Fuganti, C., Ghiringhelli, D. and Grasselli, P. (1975) “Stereochemical Course of the Reduction of Cinnamaldehyde and Cinnamyl alcohol by Fermenting Bakers’ Yeast.” J. Chem. Soc. Chem. Commun., 846–847.

    Google Scholar 

  • Fuganti, C. and Grasselli, P. (1979) “Efficient Stereoselective Synthesis of Natural α-Tocopherol.” J. Chem. Soc. Chem. Commun. 1979, 995.

    Article  Google Scholar 

  • Fuganti, C. and Grasselli, P. (1982) “Synthesis of the C14-Chromanyl Moiety of Natural α-Tocopherol (Vitamin E).” J. Chem. Soc. Chem. Comm., 205–206.

    Google Scholar 

  • Fuganti, C., Grasselli, P., Servi, S. and Högberg, H.-E. (1988) “Bakers’ Yeast Mediated Preparation of (S)-3-(2-Furyl)-2-methylpropan-1-ol, a Bifunctional Chiral C5 Isoprenoid Synthon: Synthesis of (4R,8R)-4,8-Dimethyldecanal, a Pheromone of Tribolium castaneum.” J. Chem. Soc. Perkin Trans. I, 3061–3065.

    Google Scholar 

  • Fukumasa, M., Furuhashi, K., Umezawa, J., Takahashi, O. and Hirai, T. (1991) “Asymmetric Synthesis of a-methyl carboxylic acid derivatives. Stereochemistry in acidic ring opening of epoxides.” Tetrahedron Letters, 32, 1059–1062.

    Article  CAS  Google Scholar 

  • Furuhashi. K. (1989) “Preparation of optically active 2-alkyl-l-alkanols, useful as intermediates for drugs, agrochemicals and liquid crystals” Jpn Kokai Tokkyo Koho, Jap. Pat. 01100138. Chemical Abstr., 111, 232077u.

    Google Scholar 

  • Genet, J.P., Mallart, S.; Pinel, C., Juge, S. and Lafitte, J.A. (1991) “General Syntheses of nvel ruthenium catalysts and their use in asymmetric hydrogenation.” Tetrahedron Asym., 2, 43–46.

    Article  CAS  Google Scholar 

  • Goodhue C.T. and Schaeffer (1971) “Preparation ofL(+)-β-hydroxyisobutyric acid by bacterial oxidation of isobutyric acid.” Biotechn. Bioeng., 13, 203–214.

    Article  CAS  Google Scholar 

  • Gramatica, P., Ranzi, B. M. and Manitto, P. (1981) “Reduction of Cinnamyl Alcohols and Cinnamaldehydes by Saccharomyces cerevisisae.” Bioorg. Chem. 10, 22–28.

    Article  CAS  Google Scholar 

  • Gramatica, P., Manitto, P. and Poli, L. (1985a) “Chiral Synthetic intermediates via Asymmetric hydrogenation of α-Methyl- α,β-unsaturated Aldehydes by Bakers’ Yeast.” J. Org. Chem. 1985, 50, 4625.

    Google Scholar 

  • Gramatica, P., Giardina, G., Speranza, G. and Manitto, P. (1985b) “Baker’s yeast hydrogenation of carbonyl activated double bonds. Enantioselective synthesis of the (S)-form of the dihydroterpenediol secreted by Danaus chrysippus and of a pheromone of Callosobrochus chinensis L.” Chem. Lett. 1395.

    Google Scholar 

  • Gramatica, P., Manitto, P., Monti, D. and Speranza, G. (1988) “Regio and stereoselective hydrogenation of methyl substituted pentadien-l-ols by baker’s yeast.” Tetrahedron, 44, 1299–1304.

    Article  CAS  Google Scholar 

  • Gu, Q.-M., Chen, C.-S. and Sih, C..J. (1986a) “A facile enzymatic resolution process for the preparation of (+)-S-2-(6-memoxy-2-naphthyl)propionic acid (Naproxen).” Tetrahedron Lett., 27, 1763–1766.

    Article  CAS  Google Scholar 

  • Gu, Q.-M., Reddy, D. R. and Sih, C..J. (1986b) “Bifunctional chiral synthons via biochemical methods. VIII. Optically active 3-aroylthio-2methylpropionic acids.” Tetrahedron Lett., 27, 5203–5206.

    Article  CAS  Google Scholar 

  • Gu, R.-L. and Sih, C. J. (1990) “A chemoenzymatic synthesis of the C10-C19 moiety of FK506”. Tetrahedron Lett., 31, 3283–3286.

    Article  CAS  Google Scholar 

  • Guoqiang, L., Hjalmarsson, M., Högberg, H.-E., Jernstedt, K. and Norin, T. (1984) “Asymmetric Synthesis of 2-Alkylalkanoic acids via Alkylation of Chiral Amide anions.” Acta Chem. Scand., B 38, 795–801.

    Article  Google Scholar 

  • Hirai, T., Furuhashi, K., Yoshizawa, A., Nishiyama, I. and Fukumasa, M.,(1988) “Preparation of optically active a-methylcarboxylic acids as intermediates for insect pheromones and liquid crystals” Jpn Kokai Tokkyo Koho, Jap. Pat. 63243058. Chemical Abstr., 111, 23095j.

    Google Scholar 

  • Hoffman, R. W., Ladner, W., Steinback, K., Massa, R., Schmidt, R. and Snatzke, G. Chem. Ber. 1981, 114, 2786.

    Article  Google Scholar 

  • Hedenström, E., Högberg, H.-E., Wassgren, A.-B., Bergström, G., Löfqvist, J., Hansson, B., Anderbrant, O., Bergström, G. and Löfqvist, J. (1992) “Sex Pheromone of Pine Sawflies. Chiral Syntheses of some Active Minor Components Isolated from Neodiprion sertifer and some Chiral Anaologues of Diprionyl Acetate”Tetrahedron, 48, in press.

    Google Scholar 

  • Holmberg, E., Holmquist, M., Hedenström, E., Berglund, P., Norin, T., Högberg, H.-E. and Hult, K. (1991) “Reaction Conditions for the resolution of 2-methylalkanoic acids in esterification and hydrolysis with lipase from Candida cylindracea”. Appl. Microbiol. Biotechnol., 30, 572–578.

    Google Scholar 

  • Högberg, H.-E., Hedenström, E., Wassgren, A.-B., Hjalmarsson, M., Bergström, G., Löfqvist, J. and Norin, T. (1990) “Synthesis and Gas Chromatographic Separation of the eight Stereoisomers of Diprionol and their Acetates, Components of the Sex Pheromones of Pine Sawflies” Tetrahedron, 46, 3007–3018.

    Article  Google Scholar 

  • Högberg, H.-E., Hedenström, E., Fägerhag, J. and Servi, S. (1992) “Enantioselective Synthesis of (S)-2-Methyl-1-alkanols via Bakers’ Yeast Reduction of α-Methyl-2-thiophenepropenals” J. Org. Chem., 57, 2052–2059.

    Article  Google Scholar 

  • Kawanami, Y., Ito, Y., Kitagawa, T., Taniguchi Y., Katsuki, T. and Yamaguchi, M. (1984) “Asymmetric alkylation of carboxamides by using trans-2,5-disubstituted pyrrolidines as chiral auxiliaries.” Tetrahedron Lett., 25, 857–860.

    Article  CAS  Google Scholar 

  • Leuenberger, H. G. W., Boguth, W., Barner, R., Schmid, M. and Zell, R. (1979) “Totalsynthese von naturlichem α-Tocopherol.” Helv. Chim. Acta, 62, 455.

    Article  CAS  Google Scholar 

  • Matzinger, P.K. and Leuenberger, H.G.W. (1985) “Screening for microorganisms performing the stereoselective reduction of β-formylesters.” Appl. Microbiol. Biotechn., 22, 208–210

    CAS  Google Scholar 

  • Mori, K. (1989) “Synthesis of optically active pheromones”, Tetrahedron, 45, 3233–3298

    Article  CAS  Google Scholar 

  • Nakamura, K., Miyai, T., Ushio, K., Oka, S. and Ohno, A. (1988) “Stereochemical control in microbial reduction. Part 7. Enantioselective reduction of 2-methyl-3-oxopropionate by bakers’ yeast.” Bull. Chem. Soc. Jpn. 61, 2089–2093.

    Article  CAS  Google Scholar 

  • Ngooi, T. K., Guo, Z.-W. and Sih, C.J. (1990) “Enantioselective biocatalysis — Optically-active intermediates for venturicidin synthesis”. Biocatalysis, 3, 119–128.

    Article  CAS  Google Scholar 

  • Noyori, R. (1989) “Chemical multiplication of chirality: Science and application.” Chem. Soc. Rev., 18, 187–208.

    Article  CAS  Google Scholar 

  • Ohta, T., Takaya, H., Kitamura, M., Nagai, K. and Noyori, R. (1987) “Asymmetric hydrogenation of unsaturated carboxylic acids catalyzed by BINAP-ruthenium (II) complexes.” J. Org. Chem., 52, 3174–3176

    Article  CAS  Google Scholar 

  • Oppolzer, W., Moretti, R. and Thomi, S. (1989) “Asymmetric alkylation of N-acylsultams: A general route to enantiomerically pure, crystalline C(α,α)-disubstituted carboxylic acid derivatives.” Tetrahedron Lett., 30, 5603–5606.

    Article  CAS  Google Scholar 

  • Rettiger, K., Burschka, C, Sheeben, P., Fuchs, H. and Mosandl, A. (1991) “Chiral 2-alkylbranched acids, esters and alcohols. Preparation and stereospecific flavour evaluation.” Tetrahedron Asymmetry, 2, 965–968.

    Article  Google Scholar 

  • Salaun, J. and Karkour, B. (1987) “Optically active cyclopropanols from the enzymic resolution of dimethyl a-succinates. Synthesis of chiral 2-vinylcyclobutanaones and cyclohexenones.” Tetrahedron Lett., 28, 4669–4672.

    Article  CAS  Google Scholar 

  • Santaniello, E., Ferraboschi, P., Grisenti, P. and Manzocchi A. (1991a) “α-Methyl substituted primary alcohols as model substrates for a highly enantioselective lipase-catalyzed transesterification in organic solvents”. Enzyme Microbiol. Technol., 13, 521.

    Article  Google Scholar 

  • Santaniello, E., Ferraboschi, P., Grisenti, P. and Manzocchi A. (1991b) “Enzymes in organic solvents: Enantioselective transesterification of alpha-methylsubstituted primary alcohols catalysed by a lipase”. Bioorganic Chemistry in Healthcare and Technology. Pandit U. K. Ed, Plenum Press New York 1991.

    Google Scholar 

  • Sato, T., Hanayama, K. and Fujisawa, T. (1988) “Preparation of chiral C5-building blocks for terpene synthesis by bakers’ yeast reduction of sulfur-functionalized prenyl derivatives.” Tetrahedron Lett. 1988, 29, 2197.

    Article  Google Scholar 

  • Sayo, N., Kumobayashi, H., Teketomi, T. and Akutagawa, S.(1988) “Preparation of ruthenium-phosphine complexes.” Eur. Pat Appl EP. 271310. Chem. Abstr. 109, 211233k

    Google Scholar 

  • Schmid, M. and Barner, R. (1979) “Total synthesis of natural α-tocopherol. 2. Formation of the side chain using (-)-S-3-methyl-γ-butyrolactone.” Helv. Chim. Acta, 62, 290.

    Google Scholar 

  • Servi, S. (1990) “Bakers’ Yeast as a Reagent in Organic synthesis.” Synthesis, 1.

    Google Scholar 

  • Sonnet, P. E. (1984) “General Approach to synthesis of chiral branched hydrocarbons in high configurational purity.” J. Chem. Ecology, 10, 771–781.

    Article  CAS  Google Scholar 

  • Sonnet, P. E. (1987) “Kinetic Resolution of aliphatic alcohols with a Fungal Lipase from Mucor miekei.” J. Org. Chem., 52, 3477–3479.

    Article  CAS  Google Scholar 

  • Sonnet, P. E. and Baillargeon, M. W. (1991) “Methyl-Branched Octanoic Acids as Substrates for Lipase-Catalyszed Reactions.” Lipids 26, 295–300.

    Article  CAS  Google Scholar 

  • Sonnet, P. E. and Gazillo, J. (1990) “Asymmetric Synthesis of 2-, 3-, and 4-methyloctanoic acids.” Org. Prep. Proced. Int., 22, 203–208.

    Article  CAS  Google Scholar 

  • Takaya, H., Ohta, T., Noyori, R, Sayo, N., Kumobayashi, H. and Akutagawa, S. (1988) “Ruthenium-binaphthylphosphine catalyzed production of optically active carboxylic acids.” Eur. Pat. Appl. EP 272787. Chem Abstr., 110, 11447w.

    Google Scholar 

  • Tanner, D. and Birgersson, C. (1991) “C2-Symmetric Aziridines as Efficient Chiral Auxiliaries.” Tetrahedron Lett., 32, 2533–2536.

    Article  CAS  Google Scholar 

  • VanMiddlesworth, F., Wang, Y. F., Zhou B.-n., DiTullio, D. and Sih, C. J. (1985) “Bifunctional chiral synthons via biochemical methods. VI. C5 isoprenoid units.” Tetrahedron Lett., 26, 961–964.

    Article  Google Scholar 

  • Wang, Y.-F., Chen, C.-S., Girdaukas, G. and Sih, C.J. (1984) “Bifunctional Chiral Synthons via Biochemical Methods. 3. Optical purity Enhancement in Asymmetric Enzymatic Catalysis.” J. Am. Chem. Soc., 106, 3695–3696.

    Article  CAS  Google Scholar 

  • Ward, O. P. and Young, C. S. (1990) “Reductive biotransformations of organic compounds by cells or enzymes of yeast.” Enzyme Microb. Technol., 12, 482.

    Article  CAS  Google Scholar 

  • Xie, Z.-F. (1991) “Pseudomonas fluorescens Lipase in Asymmetric Synthesis”Tetrahedron Asym., 2, 733–750.

    Article  CAS  Google Scholar 

  • Yamamoto, N., Murata, M., Morimoto, T. and Achiwa, K. (1991) “Asymmetric reaction catalyzed by chiral metal complexes. XLIV. Synthesis of axially dissymmetric Biphenylphosphine ligands, bimops and asymmetric hydrogenations of β-ketoester and α,β-unsaturated carboxylic acid catalyzed by their ruthenium (II) complexes.” Chem Pharm. Bull., 39, 1085–1087

    Article  CAS  Google Scholar 

  • Züger, M.F, Giovannini, F. and Seebach, D. (1983) “Preparation of Ethyl (R)-(-)-Hydroxy-2-methylpropanoate by Yeast Reduction of Ethyl-α-formylpropanoate.” Angew.Chem. Int Ed Engl., 22, 1012.

    Article  Google Scholar 

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Högberg, HE. (1992). Approaches to 2-Methyl-1-Alkanols of High Enantiomeric Purities Via Enzyme Mediated Reactions. In: Servi, S. (eds) Microbial Reagents in Organic Synthesis. NATO ASI Series, vol 381. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-2444-7_32

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  • DOI: https://doi.org/10.1007/978-94-011-2444-7_32

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