Biotransformations Family Clustering of Baeyer–Villiger Monooxygenases Based on Protein Sequence and Stereopreference** Marko D. Mihovilovic,* Florian Rudroff, Birgit Grötzl, Peter Kapitan, Radka Snajdrova, Joanna Rydz, and Robert Mach Since its discovery by Adolf von Baeyer and Victor Villiger in 1899, [1] the oxidation process later named after the two scientists has become a powerful tool in synthesis to break carbon–carbon bonds in an oxygen-insertion process. [2] The regiochemistry of the reaction is governed by predictable [*] Prof. Dr. M. D. Mihovilovic, Dipl.-Ing. F. Rudroff, Dipl.-Ing. B. Grötzl, Dipl.-Ing. P. Kapitan, MSc R. Snajdrova, MSc J. Rydz Institute of Applied Synthetic Chemistry Marie Curie Training Site GEMCAT Vienna University of Technology Getreidemarkt 9/163-OC, 1060 Wien (Austria) Fax: (+ 43) 1-58801-15499 E-mail: mmihovil@pop.tuwien.ac.at Prof. Dr. R. Mach Institute of Chemical Engineering Vienna University of Technology Wien (Austria) [**] Financial support by the European Commission under the Human Potential Program of FP-5 (contract no. HPMT-CT-2001-00243) and by the Austrian Science Fund (FWF; project no. P16373) is gratefully acknowledged. The authors thank Dr. Pierre E. Rouviere (E.I. DuPont Company) for supporting this project by the generous donation of six Escherichia coli expression systems for Baeyer– Villiger monooxygenases. Assistance by Dr. Erwin Rosenberg (Vienna University of Technology) during the determination of enantiomeric purity and by Dr. Christian Hametner (Vienna University of Technology) for NMR-based structure analysis is acknowledged. Supporting Information for this article is available on the WWW under http://www.angewandte.org or from the author. Angewandte Chemie 3609 Angew. Chem. Int. Ed. 2005, 44, 3609 –3613 DOI: 10.1002/anie.200462964  2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim