catalysts Biocatalysis and Pharmaceuticals A Smart Tool for Sustainable Development Edited by Andrés R. Alcàntara Printed Edition of the Special Issue Published in Catalysts www.mdpi.com/journal/catalysts Biocatalysis and Pharmaceuticals Biocatalysis and Pharmaceuticals A Smart Tool for Sustainable Development Special Issue Editor Andr´es R. Alc´antara MDPI • Basel • Beijing • Wuhan • Barcelona • Belgrade Special Issue Editor Andres´ R. Alcantara´ Complutense University Spain Editorial Office MDPI St. Alban-Anlage 66 4052 Basel, Switzerland This is a reprint of articles from the Special Issue published online in the open access journal Catalysts (ISSN 2073-4344) from 2018 to 2019 (available at: https://www.mdpi.com/journal/catalysts/special issues/biocatalysis pharmaceuticals). For citation purposes, cite each article independently as indicated on the article page online and as indicated below: LastName, A.A.; LastName, B.B.; LastName, C.C. Article Title. Journal Name Year, Article Number, Page Range. ISBN 978-3-03921-708-3 (Pbk) ISBN 978-3-03921-709-0 (PDF) c 2019 by the authors. Articles in this book are Open Access and distributed under the Creative Commons Attribution (CC BY) license, which allows users to download, copy and build upon published articles, as long as the author and publisher are properly credited, which ensures maximum dissemination and a wider impact of our publications. The book as a whole is distributed by MDPI under the terms and conditions of the Creative Commons license CC BY-NC-ND. Contents About the Special Issue Editor ...................................... vii Andr´esR. Alc´antara Biocatalysis and Pharmaceuticals: A Smart Tool for Sustainable Development Reprinted from: Catalysts 2019, 9, 792, doi:10.3390/catal9100792 ................... 1 Ra ´ulBenito-Arenas, Sandra G. Z´arate,Julia Revuelta and Agatha Bastida Chondroitin Sulfate-Degrading Enzymes as Tools for the Development of New Pharmaceuticals Reprinted from: Catalysts 2019, 9, 322, doi:10.3390/catal9040322 ................... 9 Pilar Hoyos, Vittorio Pace and Andr´esR. Alc´antara Biocatalyzed Synthesis of Statins: A Sustainable Strategy for the Preparation of Valuable Drugs Reprinted from: Catalysts 2019, 9, 260, doi:10.3390/catal9030260 ................... 28 Aicha Kriaa, M´elanieBourgin, H´elaMkaouar, Amin Jablaoui, Nizar Akermi, Souha Soussou, Emmanuelle Maguin and Moez Rhimi Microbial Reduction of Cholesterol to Coprostanol: An Old Concept and New Insights Reprinted from: Catalysts 2019, 9, 167, doi:10.3390/catal9020167 ................... 60 P. Santos-Moriano, P. Kidibule, N. M´ıguez, L. Fern´andez-Arrojo, A.O. Ballesteros, M. Fern´andez-Lobatoand F.J. Plou Tailored Enzymatic Synthesis of Chitooligosaccharides with Different Deacetylation Degrees and Their Anti-Inflammatory Activity Reprinted from: Catalysts 2019, 9, 405, doi:10.3390/catal9050405 ................... 70 Shuai Yuan, Yan-Li Xu, Yan Yang and Jian-Qiang Kong OcUGT1-Catalyzed Glucosylation of Sulfuretin Yields Ten Glucosides Reprinted from: Catalysts 2018, 8, 416, doi:10.3390/catal8100416 ................... 82 Abel Mu ˜niz-Mouro, Beatriz Gull´on, Thelmo A. L ´u-Chau, Mar´ıa Teresa Moreira, Juan M. Lema and Gemma Eibes Laccase Activity as an Essential Factor in the Oligomerization of Rutin Reprinted from: Catalysts 2018, 8, 321, doi:10.3390/catal8080321 ................... 91 Carlos M. Verdasco-Mart´ın,Lea Echevarrieta and Cristina Otero Advantageous Preparation of Digested Proteic Extracts from Spirulina platensis Biomass Reprinted from: Catalysts 2019, 9, 145, doi:10.3390/catal9020145 ...................106 Andrea Pinto, Immacolata Serra, Diego Romano, Martina Letizia Contente, Francesco Molinari, Fabio Rancati, Roberta Mazzucato and Laura Carzaniga Preparation of Sterically Demanding 2,2-Disubstituted-2-Hydroxy Acids by Enzymatic Hydrolysis Reprinted from: Catalysts 2019, 9, 113, doi:10.3390/catal9020113 ...................121 Marco Rabuffetti, Teodora Bavaro, Riccardo Semproli, Giulia Cattaneo, Michela Massone, Carlo F. Morelli, Giovanna Speranza and Daniela Ubiali Synthesis of Ribavirin, Tecadenoson, and Cladribine by Enzymatic Transglycosylation Reprinted from: Catalysts 2019, 9, 355, doi:10.3390/catal9040355 ...................132 v Daniel Gonz´alez-Mart´ınez, Nerea Fern´andez-S´aez, Carlos Cativiela, Joaqu´ın M. Campos and Vicente Gotor-Fern´andez Development of Biotransamination Reactions towards the 3,4-Dihydro-2H-1,5- benzoxathiepin-3-amine Enantiomers Reprinted from: Catalysts 2018, 8, 470, doi:10.3390/catal8100470 ...................144 Jen˝oGacs, Wuyuan Zhang, Tanja Knaus, Francesco G. Mutti, Isabel W.C.E. Arends and Frank Hollmann A Photo-Enzymatic Cascade to Transform Racemic Alcohols into Enantiomerically Pure Amines Reprinted from: Catalysts 2019, 9, 305, doi:10.3390/catal9040305 ...................156 vi About the Special Issue Editor Andr´es R. Alc´antara (Professor). During his Ph.D. thesis at the University of Cordoba´ (Spain), thanks to an FPI Scholarship and all through his postdoctoral stay (working contract as Visiting Research Fellow) at the University of Kent at Canterbury, U.K., (three periods between 1989 and 1991, under the supervision of the late Professor A. Williams), his research line has been focused on Biotransformations and Applied Biocatalysis in Organic Chemistry, specifically, in the preparation of enantiomerically pure compounds as chemical drug precursors, using mainly proteases, lipases and alcohol dehydrogenases, either native or immobilized. On the other hand, his work fits perfectly within Sustainable Chemistry, since he has applied these biocatalysts mainly in sustainable bio-solvents, which generates a very beneficial synergy from the point of view of the sustainability of the processes. This background has reported him more than 100 scientific papers, reviews, monographs and book chapters and more than 100 communications in national and international congresses. He has also actively participated in more than 30 funded projects, contracts and research activities by different organizations, being the Principal Investigator in 6 of them. Currently, he is the Director of TransBioMat, a new research group also at UCM, still in the process of evaluation, together with researchers from the Institute of Biofunctional Studies. In this Complutense University, where he has developed his research work (briefly reviewed so far) and also his teaching work from 1989 to the present, he is Full Professor of Organic Chemistry since March 2018. Finally, as one of the first partners of SEBiot (Spanish Society of Biotechnology), he was, consecutively, Coordinator of the Section of Applied Biocatalysis (2004–2007), Member of the Board of Directors (September 2004–September 2006), Secretary Elect (September 2006–September 2008) and, from 2008 to 2012, Secretary General. Last December 2018 he was elected member of the Scientific Board of the Section on Applied Biocatalysis (ESAB) of the European Federation of Biotechnology (EFB). vii catalysts Editorial Biocatalysis and Pharmaceuticals: A Smart Tool for Sustainable Development AndrésR.Alcántara Department of Chemistry in Pharmaceutical Sciences, Section of Organic and Pharmaceutical Chemistry, Faculty of Pharmacy, Complutense University of Madrid, Plaza de Ramón y Cajal, s/n, E-28040 Madrid, Spain; [email protected]; Tel./Fax: +34-91-394-1820 Received: 16 September 2019; Accepted: 19 September 2019; Published: 23 September 2019 1. Background Biocatalysis is the term used to describe the application of any type of biocatalyst (enzymes, as isolated preparations of wild-type or genetically modified variants, or whole cells, either as native cells or as recombinant expressed proteins inside host cells) in a given synthetic schedule [1]. One type of applied biocatalysis, also called a biotransformation [2], takes advantage of the excellent enzymatic precision inherent to its use, in terms of chemoselectivity, regioselectivity, or stereoselectivity. The use of biotransformations has increased considerably in recent decades, complementing classical chemical synthesis in multiple industries, mainly for the preparation of pharmaceuticals [1,3–18], fine chemicals [19–21] or food products [22–24]. Additionally, and based on the principles and metrics of green chemistry [25–29] and sustainable chemistry [30–37], biocatalysis fits perfectly into this framework; in fact, biocatalyzed procedures are highly efficient, economical, and generate less waste than conventional organic syntheses [38–46]. As such, the interest in the application of biocatalysis within the pharma industry is not surprising, as this industry is by far the biggest waste producer [43,46–50]. Furthermore, as biotransformations are generally conducted under approximately the same temperature and pressure conditions, the possibility of carrying out coupled cascade processes is enabled, providing additional economic and environmental advantages [51–58]. Finally, most biotransformations can be easily developed in standard multipurpose batch reactors without requiring costly specific devices, such as high-pressure equipment [59,60], allowing the costless implementation of continuous processes [21,44,61–63]. In recent decades, the increase of the impact of biocatalysis within the pharma industry has not been linear. In fact, it was relatively minor until the last two decades, when a clear increase (the third wave of biocatalysis [64]) was caused by the popularization of the genetic manipulation of biocatalysts by directed evolution [15,65–75], a method involving