Chemoenzymatic syntheses

Chemoenzymatic synthesis of chiral biologically active heterocycles 97F307. 

Figure 6.7 Chemoenzymatic synthesis of the E-ring portion of camptothecin.

Figure 6.9 Chemoenzymatic synthesis of amino acids via desymmetrization of malonates.

Figure 6.62 Chemoenzymatic synthesis of natural products from the p-benzoquinone-cyclopentadiene adduct.

The enantioconvergent biohydrolysis of sterically demanding trisubstituted oxiranes has also been reported [189,190]. For instance, the enantioconvergent hydrolysis of a trisubstituted rac-epoxide (Figure 6.70) was a key step in the chemoenzymatic synthesis of a volatile constituent of the beer aroma [190]. 

The chemoenzymatic synthesis of the analgesic U-(—)-50,488 [41] and new C2-symmetric bisaminoamide ligands derived from N,N-disubstituted trans-cyclohexane, ,2-diamine [41] has been possible by a CALB-catalyzed resolution using ethyl acetate as solvent and acyl donor [42]. 

Figure 10.43 Chemoenzymatic synthesis of a chiral eopthilone A building block based on an aldolization reaction.

Poly(malic acid) is a biodegradable and bioadsorbable water-soluble polyester having a carboxylic acid in the side chain. The chemoenzymatic synthesis of poly(malic acid) was achieved by the lipase-catalyzed polymerization of benzyl (3-malolactonate, followed by the debenzylation. The molecular weight of poly(benzyl (3-malolactonate) increased on copolymerizafion with a small amount of (3-PL using lipase CR catalyst. ... 

Chemoenzymatic synthesis of alkyds (oil-based polyester resins) was demonstrated. PPL-catalyzed transesterification of triglycerides with an excess of 1,4-cyclohexanedimethanol mainly produced 2-monoglycerides, followed by thermal polymerization with phthalic anhydride to give the alkyd resins with molecular weight of several thousands. The reaction of the enzymatically obtained alcoholysis product with toluene diisocyanate produced the alkyd-urethane. 

Gou, D.M., Liu, Y.C., Chen, C.S. (1993) A Practical Chemoenzymatic Synthesis ofthe Taxol C-13 Side Chain N-Benzoyl-(2R,3S)-3-phenylisoserine. Journal of Organic Chemistry, 58, 1287-1289. 

Johnson, D.V. and Griengl, H. (1997) The chemoenzymatic synthesis of (5)-13-hydroxyoctadeca-(9Z,ll )-dienoic acid using the hydroxynitrile lyase from Hevea brasiliensis. Tetrahedron, S3, 617-624. 

Figure 7.36 Chemoenzymatic synthesis of A-(phosphonomethyl)glycine (glyphosate)...

Boyd, D.R., Sharma, N.D., Bowers, N.I. et al. (1996) Stereoselective dioxygenase-catalyzed benzylic hydroxyl-ation at prochiral methylene groups in the chemoenzymatic synthesis of enantiopure vicinal aminoindanols. Tetrahedron Asymmetry, , 1559-1562. 

Mori K (2000) Chemoenzymatic synthesis of pheromones, terpenes, and other bioregulators. In Patel RN (ed) Stereoselective biocatalysis. Marcel Dekker, New York, p 59... 

Chemoenzymatic synthesis of biodegradable poly(malic acid) was performed by lipase-catalyzed polymerization of benzyl /J-malolactone, followed by the debenzylation [72]. The addition of a small amount of /J-PL (17 mol % for the monomer) increased Mw up to 3 x 104 [73]. 

Payre, N., Cottaz, S. and Driguez, H. (1995). Chemoenzymatic synthesis of a modified pentasaccharide as a specific substrate for a sensitive assay of alpha-amylase by fluorescence quenching. Angew. Chem. Int. Ed. Engl. 34, 1239-1241. 

H. Hellmuth, L. Hillringhaus, S. Hobbel, S. Kralj, L. Dijkhuizen, and J. Seibel, Highly efficient chemoenzymatic synthesis of novel branched thiooligosacchar-ides by substrate direction with glucansucrases, Chembiochem, 8 (2007) 273-276. 

D. Zanini and R. Roy, Chemoenzymatic synthesis and lectin binding properties of dendritic /V-acetyllactosaniine, Bioconjug. Chem., 8 (1997) 187-192. 

Scheme 1. Chemoenzymatic synthesis of a Rhinovirus protease inhibitor...

Scheme 4. Chemoenzymatic synthesis of Ruprintrivir by enzymatic reduction...

Scheme 10. Chemoenzymatic synthesis of pregabalin by overcoming product inhibition...

Hu S, Kelly S, Lee S, Tao J, Flahive E (2006) Efficient chemoenzymatic synthesis of Pelitrexol via enzymatic differentiation of a remote stereocenter. Org Lett 8 1653-1655... 

Chemoenzymatic Synthesis of Fluorescent N-Ras Lipopeptides and Their Use in Membrane Localization Studies In Vivo, H. Waldmann, M. Schelhaas, E. Nagele, J. Kuhlmann, A. Wittinghofer, H. Schroeder, J. R. Silvius, Angew. Chem. 1997,109, 2334-2337, Angew. Chem. Int. Ed. 1997,36,2238-2241. 

Chemoenzymatic Synthesis of a Characteristic Glyco-phosphopeptide from the Transactivation Domain of the Serum Response Factor, J. Sander H. Waldmann, Angew. Chem 1999, 111, 1337-1339, Angew. Chem Int. Ed. 1999,38,1250-1252... 

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