IJOC  Vol.5 No.4 , December 2015
Chemoenzymatic Synthesis of an Enantiomerically Enriched Bicyclic Carbocycle Using Candida parapsilosis ATCC 7330 Mediated Enantioselective Hydrolysis
Abstract: Enantiomerically enriched (R)-1-(2-bromocycloalkenyl)-3-buten-1-ol and its derivatives were obtained via enantioselective hydrolysis [resolution] with good enantioselectivities (E = 31 to >500) using Candida parapsilosis ATCC 7330. The various reaction parameters were optimized for enantioselective hydrolysis to achieve high enantiomeric excess (ee) and conversions. Among the substrates tested, (RS)-1-(2-bromocyclohex-1-en-1-yl) but-3-yn-1-yl acetate was hydrolysed by the biocatalyst in 12 h to the corresponding (R)-alcohol in 49% conversion and >99 ee. The optically pure allylic alcohol thus obtained was used as a chiral starting material for the synthesis of an enantiomerically enriched bicyclic alcohol effectively establishing achemoenzymatic route.
Cite this paper: Saravanan, T. , Chadha, A. , Dinesh, T. , Palani, N. and Balasubramanian, S. (2015) Chemoenzymatic Synthesis of an Enantiomerically Enriched Bicyclic Carbocycle Using Candida parapsilosis ATCC 7330 Mediated Enantioselective Hydrolysis. International Journal of Organic Chemistry, 5, 271-281. doi: 10.4236/ijoc.2015.54027.

[1]   Bellemin-Laponnaz, S., Tweddell, J., Ruble, J.C., Breitling, F.M. and Fu, G.C. (2000) The Kinetic Resolution of Allylic Alcohols by a Non-Enzymatic Acylation Catalyst; Application to Natural Product Synthesis. Chemical Communications, 1009-1010.

[2]   Hoveyda, A.H., Evans, D.A. and Fu, G.C. (1993) Substrate-Directable Chemical Reactions. Chemical Reviews (Washington DC), 93, 1307-1370.

[3]   Fontana, A., d’Ippolito, G., D’Souza, L., Mollo, E. and Parameswaram, P.S. (2001) New Acetogenin Peroxides from the Indian Sponge Acarnus bicladotylota. Journal of Natural Products, 64, 131-133.

[4]   Roush, W.R. and Sciotti, R.J. (1998) Enantioselective Total Synthesis of (-)-Chlorothricolide via the Tandem Inter- and Intramolecular Diels-Alder Reaction of a Hexaenoate Intermediate. Journal of the American Chemical Society, 120, 7411-7419.

[5]   Marino, J.P., McClure, M.S., Holub, D.P., Comasseto, J.V and Tucci, F.C. (2002) Stereocontrolled Synthesis of (-)- Macrolactin A. Journal of the American Chemical Society, 124, 1664-1668.

[6]   BouzBouz, S., Pradaux, F., Cossy, J., Ferroud, C. and Falguieres, A. (2000) Enantioselective Synthesis of Propargylic Alcohols by Addition of Enantiopure Cyclopentadienyldialkoxyallyltitanium Complexes to Acetylenic Aldehydes. Tetrahedron Letters, 41, 8877-8880.

[7]   Frantz, D.E., Faessler, R. and Carreira, E.M. (2000) Facile Enantioselective Synthesis of Propargylic Alcohols by Direct Addition of Terminal Alkynes to Aldehydes. Journal of the American Chemical Society, 122, 1806-1807.

[8]   Pu, L. and Yu, H.-B. (2001) Catalytic Asymmetric Organozinc Additions to Carbonyl Compounds. Chemical Reviews (Washington DC), 101, 757-824.

[9]   Nakamura, S., Kusuda, S., Kawamura, K. and Toru, T. (2002) Preparation of Optically Pure Propargylic and Allylic Alcohols from 2-(Trimethylsilyl)vinyl Sulfoxides as a Chiral Ethynyl Anion Synthon: Computational Studies on Elimination Reaction of 2-(Trimethylsilyl)vinyl Sulfoxides. Journal of Organic Chemistry, 67, 640-647.

[10]   Birman, V.B. and Jiang, H. (2005) Kinetic Resolution of Alcohols Using a 1,2-Dihydroimidazo[1,2-a]quinoline Enantioselective Acylation Catalyst. Organic Letters, 7, 3445-3447.

[11]   Rotticci, D., Norin, T. and Hult, K. (2000) Mass Transport Limitations Reduce the Effective Stereospecificity in Enzyme-Catalyzed Kinetic Resolution. Organic Letters, 2, 1373-1376.

[12]   Vedejs, E. and Daugulis, O. (1999) 2-Aryl-4,4,8-trimethyl-2-phosphabicyclo[3.3.0]octanes: Reactive Chiral Phosphine Catalysts for Enantioselective Acylation. Journal of the American Chemical Society, 121, 5813-5814.

[13]   Onaran, M.B. and Seto, C.T. (2003) Using a Lipase as a High-Throughput Screening Method for Measuring the Enantiomeric Excess of Allylic Acetates. Journal of Organic Chemistry, 68, 8136-8141.

[14]   Therasse, P., Arbuck, S.G., Eisenhauer, E.A., Wanders, J. and Kaplan, R.S. (2000) New Guidelines to Evaluate the Response to Treatment in Solid Tumors. European Organization for Research and Treatment of Cancer, National Cancer Institute of the United States, National Cancer Institute of Canada. Journal of the National Cancer Institute, 92, 205-216.

[15]   Trost, B.M. and Pinkerton, A.B. (2000) A New Strategy for Cyclopente-none Synthesis. Organic Letters, 2, 1601-1603.

[16]   Herrmann, J.L., Richman, J.E. and Schlessinger, R.H. (1973) Novel Linch-Pin Construction of Dihydrojasmone. High Yield Synthesis of Cis-Jasmone. Tetrahedron Letters, 14, 3275-3278.

[17]   Mathew, J. and Alink, B. (1990) A Novel Route to Substituted Cyclopent-2-en-1-one; Application to the Synthesis of Cis-Jasmone and Dihydrojasmone. Journal of the Chemical Society, Chemical Communications, No. 9, 684-686.

[18]   Mikolajczyk, M. and Balczewski, P. (1987) Methylenomycin B: A New Synthesis from a β-Keto Phosphonate. Synthesis, 1987, 659-661.

[19]   Smith III, A.B., and Boschelli, D. (1983) Stereocontrolled Total Synthesis of (±)-Xanthocidin, Two Diastereomers, (±)-Epixanthocidin and (±)-β-Isoxanthocidin, and (±)-Dedihydroxy-4,5-didehydroxanthocidin, a Likely Biosynthetic Precursor. The Journal of Organic Chemistry, 48, 1217-1226.

[20]   Ray, D., Mal, S.K. and Ray, J.K. (2005) Palladium-Catalyzed Novel Cycloisomerization: An Unprecedented Domino Oxidative Cyclization towards Substituted Carbocycles. Synlett, 2005, 2135-2140.

[21]   Ray, D., Nasima, Y., Sajal, M.K., Ray, P. and Urinda, S. (2013) Palladium-Catalyzed Intramolecular Oxidative Heck Cyclization and Its Application toward a Synthesis of (±)-β-Cuparenone Derivatives Supported by Computational Studies. Synthesis, 45, 1261-1269.

[22]   Vedejs, E. and MacKay, J.A. (2001) Kinetic Resolution of Allylic Alcohols Using a Chiral Phosphine Catalyst. Organic Letters, 3, 535-536.

[23]   Dinesh, T.K., Palani, N. and Balasubramanian, S. (2015) Intramolecular Radical Cyclization of Vinyl, Aryl and Alkyl Halides Using Catalytic Amount of Bis-tri-n-butyltin Oxide/Sodium Borohydride: A Novel Entry to Functionalized Carbocycles. Synlett, 26, 1055-1058.

[24]   Hart, D.J. (1984) Free-Radical Carbon-Carbon Bond Formation in Organic Synthesis. Science, 223, 883-887.

[25]   Stork, G. and Mook Jr., R., (1983) Vinyl Radical Cyclization. 2. Dicyclization via Selective Formation of Unsaturated Vinyl Radicals by Intramolecular Addition to Triple Bonds. Applications to the Synthesis of Butenolides and Furans. Journal of the American Chemical Society, 105, 3720-3722.

[26]   Lee, D., Huh, E.A., Kim, M.-J., Jung, H.M. and Koh, J.H. (2000) Dynamic Kinetic Resolution of Allylic Alcohols Mediated by Ruthenium- and Lipase-Based Catalysts. Organic Letters, 2, 2377-2379.

[27]   Kadnikova, E.N. and Thakor, V.A. (2008) Enantioselective Hydrolysis of 1-Arylallyl Acetates Catalyzed by Candida antarctica Lipase. Tetrahedron: Asymmetry, 19, 1053-1058.

[28]   Marques, FA., Oliveira, M.A., Frensch, G., Sales Maia, B.H.L.N. and Barison, A. (2011) Highly Efficient Kinetic Resolution of Allylic Alcohols with Terminal Double Bond. Letters in Organic Chemistry, 8, 696-700.

[29]   Chen, P. and Xiang, P. (2011) Kinetic Resolution of Allylic Alcohols via Stereoselective Acylation Catalyzed by Lipase PS-30. Tetrahedron Letters, 52, 5758-5760.

[30]   Lau, R.M., van Rantwijk, F., Seddon, K.R. and Sheldon, R.A. (2000) Lipase-Catalyzed Reactions in Ionic Liquids. Organic Letters, 2, 4189-4191.

[31]   Reetz, M.T. (2002) Lipases as Practical Biocatalysts. Current Opinion in Chemical Biology, 6, 145-150.

[32]   Palani, N., Chadha, A. and Balasubramanian, K.K. (1998) Mechanism of Lithium Perchlorate/Diethyl Ether-Catalyzed Rearrangement of α- and β-Endo- and -Exo-Dicyclopentadienyl Vinyl Ethers: Use of Deuterium Labeling and a Chiral Probe. The Journal of Organic Chemistry, 63, 5318-5323.

[33]   Vidya, P. and Chadha, A (2010) Pseudomonas cepacia Lipase Catalyzed Esterification and Transesterification of 3-(Furan-2-yl) Propanoic Acid/Ethyl Ester: A Comparison in Ionic Liquids vs Hexane. Journal of Molecular Catalysis B: Enzymatic, 65, 68-72.

[34]   McCubbin, J.A., Maddess, M.L. and Lautens, M. (2008) Enzymatic Resolution of Chlorohydrins for the Synthesis of Enantiomerically Enriched 2-Vinyloxiranes. Synlett, 2008, 289-293.

[35]   Takabe, K., Yamada, T., Miyamoto, T. and Mase, N. (2008) Cyclization of N,N-Diethylgeranylamine N-Oxide in One-Pot Operation: Preparation of Cyclic Terpenoid-Aroma Chemicals. Tetrahedron Letters, 49, 6016-6018.

[36]   Chadha, A. and Baskar, B. (2002) Biocatalytic Deracemization of α-Hydroxy Esters: High Yield Preparation of (S)-Ethyl 2-Hydroxy-4-phenylbutanoate from the Racemate. Tetrahedron: Asymmetry, 13, 1461-1464.

[37]   Baskar, B., Pandian, N.G., Priya, K. and Chadha, A. (2005) Deracemization of Aryl Substituted α-Hydroxy Esters Using Candida parapsilosis ATCC 7330: Effect of Substrate Structure and Mechanism. Tetrahedron, 61, 12296-12306.

[38]   Saravanan, T., Jana, S. and Chadha, A. (2014) Utilization of Whole Cell Mediated Deracemization in a Chemoenzymatic Synthesis of Enantiomerically Enriched Polycyclic Chromeno[4,3-b] Pyrrolidines. Organic & Biomolecular Chemistry, 12, 4682-4690.

[39]   Titu, D. and Chadha, A. (2008) Enantiomerically Pure Allylic Alcohols: Preparation by Candida parapsilosis ATCC 7330 Mediated Deracemisation. Tetrahedron: Asymmetry, 19, 1698-1701.

[40]   Mahajabeen, P. and Chadha, A. (2011) One-Pot Synthesis of Enantiomerically Pure 1,2-Diols: Asymmetric Reduction of Aromatic α-Oxo Aldehydes Catalyzed by Candida parapsilosis ATCC 7330. Tetrahedron: Asymmetry, 22, 2156- 2160.

[41]   Venkataraman, S. and Chadha, A. (2015) Preparation of Enantiomerically Enriched (S)-ethyl 3-Hydroxy 4,4,4-Trifluorobutanoate Using Whole Cells of Candida parapsilosis ATCC 7330. Journal of Fluorine Chemistry, 169, 66-71.

[42]   Sivakumari, T. and Chadha, A. (2014) Regio- and Enantio-Selective Oxidation of Diols by Candida parapsilosis ATCC 7330. RSC Advances, 4, 60526-60533.

[43]   Stella, S. and Chadha, A. (2010) Resolution of N-Protected Amino Acid Esters Using Whole Cells of Candida parapsilosis ATCC 7330. Tetrahedron: Asymmetry, 21, 457-460.

[44]   Waldinger, C., Schneider, M., Botta, M., Corelli, F. and Summa, V. (1996) Aryl Propargylic Alcohols of High Enantiomeric Purity via Lipase Catalyzed Resolutions. Tetrahedron: Asymmetry, 7, 1485-1488.

[45]   Kinoshita, M. and Ohno, A. (1996) Factors Influencing Enantioselectivity of Lipase-Catalyzed Hydrolysis. Tetrahedron, 52, 5397-5406.

[46]   Szymanski, W. and Ostaszewski, R. (2007) Chemoenzymatic Synthesis of Enantiomerically Enriched α-Hydroxyamides. Journal of Molecular Catalysis B: Enzymatic, 47, 125-128.

[47]   Malkov, A.V., Barlog, M., Jewkes, Y., Mikusek, J. and Kocovsky, P. (2011) Enantioselective Allylation of α,β-Unsaturated Aldehydes with Allyltrichlorosilane Catalyzed by METHOX. The Journal of Organic Chemistry, 76, 4800-4804.

[48]   Rakels, J.L.L., Straathof, A.J.J. and Heijnen, J.J. (1993) A Simple Method to Determine the Enantiomeric Ratio in Enantioselective Biocatalysis. Enzyme and Microbial Technology, 15, 1051-1056.