Practical Methods for Biocatalysis and Biotransformations 3

Dr John Whittall, Centre of Excellence for Biocatalysis, Biotransformations and Biocatalytic Manufacture (CoEBio3), Manchester Interdisciplinary Biocentre, University of Manchester, UK. Dr Peter W Sutton, Senior Scientist, GlaxoSmithKline Research and Development Limited, UK. Dr Wolfgang Kroutil, Department of Chemistry, Organic and Bioorganic Chemistry, University of Graz, Austria.

List of Contributors Abbreviations 1 Considerations for the Application of Process Technologies for Laboratory and Pilot-Scale Biocatalysis for Chemical Synthesis Hemalata Ramesh, Mathias Nordblad, John Whittall and John M. Woodley 2 Cytochrome P450 (CYP) progress in biocatalysis for synthetic organic chemistry Thomas S Moody and Steve JC Taylor 3 Use of Hydrolases and Related Enzymes for Synthesis 3.1 Continuous-flow reactor-based enzymatic synthesis of phosphorylated compounds on a large scale Lara Babich, Aloysius F. Hartog, Michael A. van der Horst, and Ron Wever 3.2 Deracemisation of sec-alcohols via enantio-convergent hydrolysis of rac-sulfate esters Michael Toesch, Markus Schober and Kurt Faber 3.3 Dynamic Kinetic Resolution of a Primary Amine by an Efficient Bifunctional Pd-CALB Hybrid Catalyst. A Metalloenzyme Mimic for Enhanced Cooperative Catalysis Oscar Verho, Karl P. J. Gustafson and Jan-E. Backvall 3.4 Highly efficient dynamic kinetic resolution of secondary 1-phenylethanol derivatives using a low cost solid super acid as racemization catalyst Gang Xu, Jian-Ping Wu, Yong-Jun Chen, Liang Wang, Xiao Meng and Li-Rong Yang 3.5 Identification of new biocatalysts for the enantioselective conversion of tertiary alcohols Robert Kourist, Susanne Herter and Uwe T. Bornscheuer 3.6 Enzyme catalyzed hydrolysis of bicycloheptane diester to monoester Zhiwei Guo, Michael Kwok Y Wong, Matthew R Hickey, Bharat P Patel, Xinhua Qian and Animesh Goswami 3.7 A Double Mutant Lipase with Enhanced Activity and Enantioselectivity for Bulky Secondary Alcohols Tadashi Ema, Shusuke Kamata, Yasuko Nakano, Daiki Yoshida and Takashi Sakai 3.8 Stereoselective synthesis of b-amino acids by hydrolysis of an aryl-substituted dihydropyrimidine by hydantoinases Ulrike Engel, Christoph Syldatk and Jens Rudat 4. Non-redox Lyases and Transferases for C-C, C-O, C-S and C-N bond formation 4.1 Regioselective enzymatic carboxylation of phenols and hydroxystyrenes employing cofactor-independent decarboxylases Johannes Gross, Tamara Reiter, Christiane Wuensch, Silvia M. Glueck and Kurt Faber 4.2 Stetter Reactions Catalyzed by Thiamine Diphosphate-Dependent Enzymes Carola Dresen, Elena Kasparyan, Lydia S. Walter, Fabrizio Bonina, Simon Waltzer and Michael Muller 4.3 Asymmetric Michael-type additions of acetaldehyde to nitroolefins catalyzed by 4-oxalocrotonate tautomerase (4-OT) yielding valuable -nitroaldehydes Edzard M. Geertsema, Yufeng Miao, and Gerrit J. Poelarends 4.4 Michael-type addition of aldehydes to b-nitrostyrenes by whole cells of Escherichia coli expressing 4-oxalocrotonate tautomerase (4-OT) Tanja Narancic, Gordana Minovska, Predrag Jovanovic, Jelena Radivojevic and Jasmina Nikodinovic-Runic 4.5 Norcoclaurine synthases for the biocatalytic synthesis of tetrahydroisoquinolines Benjamin Lichman, Eleanor D. Lamming, John M. Ward and Helen C. Hailes 4.6 Streptavidin based Artificial Metallo-annulase for the Enantioselective Synthesis of Dihydroisoquinolones Todd K. Hyster, Livia Knorr, Tomislav Rovis and Thomas R. Ward 4.7 Regiospecific Benzylation of Tryptophan and Derivatives Catalyzed by a Fungal Dimethylallyl Transferase Mike Liebhold and Shu-Ming Li 4.8 Enantioselective Michael addition of water using Rhodococcus rhodochrous ATCC 17895 Bi-Shuang Chen, Verena Resch and Ulf Hanefeld 4.9 Sulfation of various compounds by an arylsulfotransferase from Desulfitobacterium hafniense and synthesis of 17b-estradiol-3-sulfate Michael A. van der Horst, Johan F. T. van Lieshout, Aleksandra Bury, Aloysius F. Hartog and Ron Wever 4.10 Asymmetric synthesis of cyclopropanes and benzosultams via enzyme-catalyzed carbenoid and nitrenoid transfer in E. coli whole-cells. Christopher C. Farwell, Hans Renata and Frances H. Arnold 4.11 Biocatalytic production of novel glycolipids Karel De Winter, Griet Dewitte, Hai Giang Tran and Tom Desmet 4.12 Enzymatic synthesis of 8-aza- and 8-aza-7-deazapurine 2 -deoxyribonucleosides Vladimir A. Stepchenko, Frank Seela, Roman S. Esipov, Anatoly I. Miroshnikov and Igor A. Mikhailopulo 4.13 Phenylalanine ammonia lyase catalyzed asymmetric hydroamination for the synthesis of L-amino acids Sarah L. Lovelock and Nicholas J. Turner 5. Oxidations 5.1 Semi-Preparative Scale Drug Metabolite Synthesis with Human Flavin Monooxygenases Steven P. Hanlon, Matthias Kittelmann and Margit Winkler 5.2 Biobased synthesis of industrially relevant nitriles by selective oxidative decarboxylation of amino acids by vanadium chloroperoxidase Andrada But, Jerome Le Notre, Elinor L. Scott, Ron Wever and Johan P. M. Sanders 5.3 Terminal oxygenation of fatty acids by a CYP153A fusion construct heterologously expressed in E. coli. Sumire Honda Malca, Daniel Scheps, Bettina M. Nestl and Bernhard Hauer 5.4 Enantioselective oxidative C C bond formation in isoquinoline alkaloids employing the berberine bridge enzyme Verena Resch, Joerg H. Schrittwieser, Wolfgang Kroutil 5.5 Oxidation of aldehydes using alcohol dehydrogenases Frank Hollmann 5.6 Monoamine oxidase catalysed deracemisation of racemic amines for the synthesis of pharmaceutical building blocks Diego Ghislieri and Nicholas J. Turner 5.7 Synthesis of (S)-amines by chemo-enzymatic deracemisation using an (R)-selective amine oxidase Rachel S. Heath, Marta Pontini, Beatrice Bechi and Nicholas J. Turner 5.8 Selective oxidation of diols into lactones under aerobic conditions using a laccase-TEMPO catalytic system in aqueous medium Alba Diaz-Rodriguez, Ivan Lavandera, Vicente Gotor-Fernandez and Vicente Gotor 6. Reductions 6.1 Tetrahydroxynaphthalene Reductase Broad Substrate Range of an NADPH-Dependent Oxidoreductase Involved in Reductive Asymmetric Naphthol Dearomatization Michael A. Schatzle, Syed Masood Husain and Michael Muller 6.2 Chemoenzymatic Synthesis of Diastereo- and Enantiomerically Pure 2,6-Disubstituted Piperidines via Regioselective Monoamination of 1,5-Diketones Robert C. Simon, Ferdinand Zepeck and Wolfgang Kroutil 6.3 Asymmetric amination of ketones employing -transaminases in organic solvents Francesco G. Mutti, Christine Fuchs and Wolfgang Kroutil 6.4 Stereoselective Synthesis of (R)-Profen Derivatives by the Enoate Reductase YqjM Thomas Classen, Jorg Pietruszka and Melanie Scholzel 6.5 Productivity improvement of the bioreduction of , -unsaturated aldehydes by coupling the in situ substrate feeding product removal (SFPR) strategy with isolated enzymes Elisabetta Brenna, Francesco G. Gatti, Daniela Monti, Fabio Parmeggiani, Alessandro Sacchetti 6.6 Reduction of imines by a recombinant whole-cell E. coli biocatalyst expressing imine reductases (IREDs) Friedemann Leipold, Shahed Hussain and Nicholas J. Turner 7. Halogenation and Dehalogenation 7.1 Site-Directed MutagenesisChanges the Regioselectivity of the Tryptophan 7-Halogenase PrnA Alexander Lang, Stefan Polnick, Tristan Nicke, Peter William, Eugenio P. Patallo, James H. Naismith and Karl-Heinz van Pee 7.2 Controlling Enantioselectivity of Halohydrin Dehalogenase from Arthrobacter sp. Strain AD2, Revealed by Structure-Guided Directed Evolution Lixia Tang and Xuechen Zhu 7.3 Enzymatic production of chlorothymol and its derivatives by halogenation of the phenolic monoterpenes thymol and carvacrol with chloroperoxidase Thomas Krieg, Laura Getrey, Jens Schrader and Dirk Holtmann 8. Cascade Reactions 8.1 Synthetic Cascades by Combining Artificial Metalloenzymes with Monoamine Oxidases (MAO-N) Marc Durrenberger, Valentin Kohler, Yvonne M. Wilson, Diego Ghislieri, Livia Knorr, Nicholas J. Turner and Thomas R. Ward 8.2 Amination of primary alcohols via a redox-neutral bio-cascade Johann H. Sattler, Michael Fuchs, Francesco G. Mutti and Wolfgang Kroutil 8.3 Biocatalytic synthesis of a diketobornane as building block for bifunctional camphor derivatives Michael Hofer, Harald Strittmatter and Volker Sieber 8.4 A Three Enzyme Catalyzed RedOx Cascade for the Production of a Carvo-Lactone Nikolin Oberleitner, Christin Peters, Jan Muschiol, Florian Rudroff, Marko D. Mihovilovic and Uwe T. Bornscheuer 8.5 Preparation of Homoallylic Alcohols via a Chemo-enzymatic One-pot Oxidation-Allylation Cascade Michael Fuchs, Markus Schober, Mathias Pickl, Wolfgang Kroutiland Kurt Faber 8.5 Cascade biotransformations via enantioselective reduction, oxidation, and hydrolysis: preparation of (R)- -lactones from 2-alkylidenecyclopentanones Ji Liu and Zhi Li 8.6 One-pot tandem enzymatic reactions for efficient biocatalytic synthesis of d-fructose-6-phosphate and analogues. Israel Sanchez-Moreno, Virgil Helaine, Nicolas Poupard,Eduardo Garcia-Junceda, Roland Wohlgemuth, Christine Guerard-Helaineand Marielle Lemaire 8.7 Efficient one-pot tandem biocatalytic process for a valuable phosphorylated C8 d-ketose: d-glycero-d-altro-2-octulose 8-phosphate. C. Guerard-Helaine, M. Debacker, P. Clapes, A. Szekrenyi, V. Helaine and M. Lemaire 8.8 Chemo-enzymatic synthesis of (S)-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid by PAL mediated amination and Pictet-Spengler cyclisation Fabio Parmeggiani, Nicholas J. Weise, Syed T. Ahmed and Nicholas J. Turner 8.9 -Transaminase/Monoamine OxidaseCascade for the Regio- and Stereoselective Synthesis of Chiral 2,5-Disubstituted Pyrrolidines Elaine O Reilly and Nicholas J. Turner Index