Enzymatic separation of epimeric 4-C-hydroxymethylated furanosugars: Synthesis of bicyclic nucleosides

• Neha Rana,
• Manish Kumar,
• Vinod Khatri,
• Jyotirmoy Maity and
• Ashok K. Prasad

Beilstein J. Org. Chem. 2017, 13, 2078–2086, doi:10.3762/bjoc.13.205

• : bicyclonucleosides; biocatalysis; lipase; Novozyme®-435; separation of epimers; Introduction Sugar-modified bicyclic nucleosides have drawn the attention of synthetic chemists because of their effect on the conformational restriction of the furanose moiety of the nucleoside [1][2][3][4][5][6][7][8][9]. The

Enzymatic synthesis of glycosides: from natural O- and N-glycosides to rare C- and S-glycosides

• Jihen Ati,
• Pierre Lafite and
• Richard Daniellou

Beilstein J. Org. Chem. 2017, 13, 1857–1865, doi:10.3762/bjoc.13.180

• . Rational mutagenesis, directed evolution, or even de novo design have dramatically broaden the applicability of enzymes in biocatalysis [7]. In the glycochemistry field, a vast array of carbohydrate-metabolizing enzymes [8] has been used to synthesize glycosides, even using multiple enzymes systems

2-Methyl-2,4-pentanediol (MPD) boosts as detergent-substitute the performance of ß-barrel hybrid catalyst for phenylacetylene polymerization

• Julia Kinzel,
• Daniel F. Sauer,
• Marco Bocola,
• Marcus Arlt,
• Tayebeh Mirzaei Garakani,
• Andreas Thiel,
• Klaus Beckerle,
• Tino Polen,
• Jun Okuda and
• Ulrich Schwaneberg

Beilstein J. Org. Chem. 2017, 13, 1498–1506, doi:10.3762/bjoc.13.148

• Biology Science Center (BioSC) and the Deutsche Forschungsgemeinschaft (DFG) through the International Research Training Group “Selectivity in Chemo- and Biocatalysis” (SeleCa), and Umicore, Frankfurt (Dr. A. Doppiu), for a generous gift of rhodium precursor.

Opportunities and challenges for the sustainable production of structurally complex diterpenoids in recombinant microbial systems

• Katarina Kemper,
• Max Hirte,
• Markus Reinbold,
• Monika Fuchs and
• Thomas Brück

Beilstein J. Org. Chem. 2017, 13, 845–854, doi:10.3762/bjoc.13.85

• Katarina Kemper Max Hirte Markus Reinbold Monika Fuchs Thomas Bruck Professorship for Industrial Biocatalysis, Department of Chemistry, Technical University of Munich, Lichtenbergstraße 4, 85748 Garching, Germany 10.3762/bjoc.13.85 Abstract With over 50.000 identified compounds terpenes are the

Synthesis of new pyrrolidine-based organocatalysts and study of their use in the asymmetric Michael addition of aldehydes to nitroolefins

• Alejandro Castán,
• Ramón Badorrey,
• José A. Gálvez and
• María D. Díaz-de-Villegas

Beilstein J. Org. Chem. 2017, 13, 612–619, doi:10.3762/bjoc.13.59

• development [1][2][3][4] and it is now considered to be the third pillar of enantioselective catalyses together with metal complex-mediated catalysis and biocatalysis. Among the different structures usually found in organocatalysis, the five-membered secondary amine structure of pyrrolidine has proven to be a

Spectral and DFT studies of anion bound organic receptors: Time dependent studies and logic gate applications

• Srikala Pangannaya,
• Neethu Padinchare Purayil,
• Shweta Dabhi,
• Venu Mankad,
• Prafulla K. Jha,
• Satyam Shinde and
• Darshak R. Trivedi

Beilstein J. Org. Chem. 2017, 13, 222–238, doi:10.3762/bjoc.13.25

• added advantage, in molecularly gated devices, Boolean logic computations could be activated by specific inputs and accurately processed through biorecognition, biocatalysis and selective chemical reactions [30]. The utilization of designed receptors in molecular logic gate applications has seen great

Sustainable catalysis

• Nicholas J. Turner

Beilstein J. Org. Chem. 2016, 12, 1778–1779, doi:10.3762/bjoc.12.167

• developments in ‘green chemistry’, especially the applications of catalytic methods, involving both chemo- and biocatalysis. The development of catalytic processes is an important current theme in organic chemistry, since it aims to reduce the environmental impact of the industrial synthesis of chemicals and

• (EFPIA). CHEM21 is a large multi-group consortium organized into six different work-packages spanning various elements of green chemistry including biocatalysis, synthetic biology and non-precious metal catalysis. In addition, there are also work packages devoted to defining current and future targets

Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162

• organocatalysts [262][263]. There are also Green chemistry approaches for Baeyer−Villiger oxidations based on enzyme-mediated processes, which are used for the preparation of chiral lactones. This type of biocatalysis is useful in synthetic chemistry and either isolated enzymes or living whole cells are applied

Artificial Diels–Alderase based on the transmembrane protein FhuA

• Hassan Osseili,
• Daniel F. Sauer,
• Klaus Beckerle,
• Marcus Arlt,
• Tomoki Himiyama,
• Tino Polen,
• Akira Onoda,
• Ulrich Schwaneberg,
• Takashi Hayashi and
• Jun Okuda

Beilstein J. Org. Chem. 2016, 12, 1314–1321, doi:10.3762/bjoc.12.124

• support by the Deutsche Forschungsgemeinschaft (DFG) through the International Research Training Group “Selectivity in Chemo- and Biocatalysis” (SeleCa), the excellence cluster “Tailor-made Fuels from Biomass” (TMFB), the JSPS Japan-German Graduate Externship Program, and Grants-in-Aid for Scientific

Unconventional application of the Mitsunobu reaction: Selective flavonolignan dehydration yielding hydnocarpins

• Guozheng Huang,
• Simon Schramm,
• Jörg Heilmann,
• David Biedermann,
• Vladimír Křen and
• Michael Decker

Beilstein J. Org. Chem. 2016, 12, 662–669, doi:10.3762/bjoc.12.66

• , Shanghai Normal University, Shanghai, P. R. China Lehrstuhl für Pharmazeutische Biologie, Institut für Pharmazie, Universität Regensburg, Universitätsstraße 31, D-93053 Regensburg, Germany Centre of Biotransformation and Biocatalysis, Institute of Microbiology, Czech Academy of Sciences, Videnska 1083

Highly stable and reusable immobilized formate dehydrogenases: Promising biocatalysts for in situ regeneration of NADH

• Barış Binay,
• Dilek Alagöz,
• Deniz Yildirim,
• Ayhan Çelik and
• S. Seyhan Tükel

Beilstein J. Org. Chem. 2016, 12, 271–277, doi:10.3762/bjoc.12.29

• , FDHIGLU and FDHIALD offer feasible potentials for in situ regeneration of NADH. Keywords: biocatalysis; Candida methylica; formate dehydrogenase; Immobead 150; regeneration of NADH; stabilization; Introduction Dehydrogenases are one of the most promising enzymes in biocatalysis since these enzymes have

Biocatalysis for the application of CO₂ as a chemical feedstock

• Apostolos Alissandratos and
• Christopher J. Easton

Beilstein J. Org. Chem. 2015, 11, 2370–2387, doi:10.3762/bjoc.11.259

• as a renewable chemical feedstock, greatly enabling a sustainable carbon bio-economy. Keywords: biocatalysis; carboxylase; CO2 transformation; formate dehydrogenase; RuBisCO; Introduction Depletion of fossil-fuel feedstocks and pollution resulting from their unsustainable processing and use

Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions

• Paul P. Kelly,
• Anja Eichler,
• Susanne Herter,
• David C. Kranz,
• Nicholas J. Turner and
• Sabine L. Flitsch

Beilstein J. Org. Chem. 2015, 11, 1713–1720, doi:10.3762/bjoc.11.186

• ], phenacetin, ethoxyresofurin and chlorzoxazone to only name a few [16]. For the current investigation we sought to develop P450cam further to expand their substrate range in biocatalysis. Our starting point was a catalytically self-sufficient form of the enzyme, previously created by fusion with the reductase

• acknowledge support from the Centre of Excellence for Biocatalysis, Biotransformations and Biocatalytic Manufacture (CoEBio3, to PPK), the FP7-PEOPLE-2011-ITN under grant agreement no. 289217 (P4fifty, to AE), the Innovative Medicines Initiative Joint Undertaking under the grant agreement no. 115360 (Chemical

Dicarboxylic esters: Useful tools for the biocatalyzed synthesis of hybrid compounds and polymers

• Ivan Bassanini,
• Karl Hult and
• Sergio Riva

Beilstein J. Org. Chem. 2015, 11, 1583–1595, doi:10.3762/bjoc.11.174

• acids and their derivatives (esters and anhydrides) have been used as acylating agents in lipase-catalyzed reactions in organic solvents. The synthetic outcomes have been dimeric or hybrid derivatives of bioactive natural compounds as well as functionalized polyesters. Keywords: biocatalysis

• esterifications of sugars and steroids, using acylating agents different from simple aliphatic acids [7][8][9]. Specifically, years ago Dordick and coworkers proposed the so-called ‘combinatorial biocatalysis’ as an approach to easily produce small libraries of derivatives of bioactive natural compounds using a

• these molecules along with the presence of multiple functional groups make their chemical manipulation difficult. This inherent “fragility” makes biocatalysis an attractive method for their derivatization. Specifically, glycosides and polyhydroxylated compounds can be selectively acylated at specific

Anomalous diffusion of Ibuprofen in cyclodextrin nanosponge hydrogels: an HRMAS NMR study

• Monica Ferro,
• Franca Castiglione,
• Carlo Punta,
• Lucio Melone,
• Walter Panzeri,
• Barbara Rossi,
• Francesco Trotta and
• Andrea Mele

Beilstein J. Org. Chem. 2014, 10, 2715–2723, doi:10.3762/bjoc.10.286

• examples of applications can be found in the recent literature, including biocatalysis [4], agriculture [5], environmental control [6] and pharmaceutical applications such as drug stabilization, enhancement of bioavailability and drug delivery [7][8][9][10][11]. A typical synthetic protocol for their

An integrated photocatalytic/enzymatic system for the reduction of CO₂ to methanol in bioglycerol–water

• Michele Aresta,
• Angela Dibenedetto,
• Tomasz Baran,
• Antonella Angelini,
• Przemysław Łabuz and
• Wojciech Macyk

Beilstein J. Org. Chem. 2014, 10, 2556–2565, doi:10.3762/bjoc.10.267

• cofactors is nicotinamide adenine dinucleotide (NAD+), a cofactor of the oxydoreductase class of enzymes. NAD+, together with its reduced form, 1,4-NADH, plays an essential role in many metabolic processes of living cells. NADH is also important in industrial biocatalysis, namely in the process of reductive

Selective allylic hydroxylation of acyclic terpenoids by CYP154E1 from Thermobifida fusca YX

• Anna M. Bogazkaya,
• Clemens J. von Bühler,
• Sebastian Kriening,
• Alexandrine Busch,
• Alexander Seifert,
• Jürgen Pleiss,
• Sabine Laschat and
• Vlada B. Urlacher

Beilstein J. Org. Chem. 2014, 10, 1347–1353, doi:10.3762/bjoc.10.137

• noted, that the enzyme used by the authors produced 8-hydroxynerol rather than 10-hydroxynerol according to their Figure 3 [41]. The use of this monooxygenase in biocatalysis is however not feasible because this enzyme is membrane bound, relies on a membrane associated cytochrome P450 reductase (CPR

Organic synthesis using photoredox catalysis

• Axel G. Griesbeck

Beilstein J. Org. Chem. 2014, 10, 1097–1098, doi:10.3762/bjoc.10.107

• synthesis is also depicted in these processes, and in recent years, enantioselective versions of these processes as well as unusual activation and coupling modes have been developed. In contrast to the “traditional” catalysis areas such as metal-, organo- and biocatalysis, photoredox catalysis (and

Biosynthesis of rare hexoses using microorganisms and related enzymes

• Zijie Li,
• Yahui Gao,
• Hideki Nakanishi,
• Xiaodong Gao and
• Li Cai

Beilstein J. Org. Chem. 2013, 9, 2434–2445, doi:10.3762/bjoc.9.281

• rare sugars has become a hot topic because of their potential applications in different fields. An important factor restricting the utilization of rare sugars is their limited availabilities, resulting from limited synthetic methods. Biocatalysis often offers advantages over chemical synthesis, because

Flow synthesis of phenylserine using threonine aldolase immobilized on Eupergit support

• Jagdish D. Tibhe,
• Hui Fu,
• Timothy Noël,
• Qi Wang,
• Jan Meuldijk and
• Volker Hessel

Beilstein J. Org. Chem. 2013, 9, 2168–2179, doi:10.3762/bjoc.9.254

• , there is indication that biocatalysis under flow conditions provided by a microreactor can result in better process control by external numbering-up in which each subunit of reaction can be examined separately with enhanced productivity [11]. Microreactors have been used in many fields of chemistry such

• intensification and biocatalysis has been reviewed [24]. Asanomi et al. have also summarized the use of microfluidic devices in biocatalysis and compared them with conventional batch reactors [25]. The advantages of enzymatic microreactors have been demonstrated both in process development and for the production

• scale [26]. Similarly these reactors can provide high throughput opportunities, reduced reaction time with high conversion efficiency and high productivity per unit reaction volume for biocatalysis in fine chemistry [27]. These advantages have been demonstrated for reactions such as hydrolysis and

C–C Bond formation catalyzed by natural gelatin and collagen proteins

• Dennis Kühbeck,
• Basab Bijayi Dhar,
• Eva-Maria Schön,
• Carlos Cativiela,
• Vicente Gotor-Fernández and
• David Díaz Díaz

Beilstein J. Org. Chem. 2013, 9, 1111–1118, doi:10.3762/bjoc.9.123

• implications from a metabolic perspective. Keywords: biocatalysis; carbon–carbon bond formation; gelatin; Henry reaction; protein; Introduction Gelatin is a mixture of hot-water-soluble proteins of high average molecular weights (50–100 kDa) derived primarily from collagen, which is the main naturally

Chemoenzymatic synthesis and biological evaluation of enantiomerically enriched 1-(β-hydroxypropyl)imidazolium- and triazolium-based ionic liquids

• Paweł Borowiecki,
• Małgorzata Milner-Krawczyk and
• Jan Plenkiewicz

Beilstein J. Org. Chem. 2013, 9, 516–525, doi:10.3762/bjoc.9.56

• biocatalysis [47][48], since solvents are able to change the activity [49][50][51] and enantioselectivity [52][53][54] of an enzyme. Conformational changes in the enzyme structure under the influence of solvent can even invert the substrate specificity and the enzyme–substrate affinity [55]. The ability to

Organocatalytic cascade aza-Michael/hemiacetal reaction between disubstituted hydrazines and α,β-unsaturated aldehydes: Highly diastereo- and enantioselective synthesis of pyrazolidine derivatives

• Zhi-Cong Geng,
• Jian Chen,
• Ning Li,
• Xiao-Fei Huang,
• Yong Zhang,
• Ya-Wen Zhang and
• Xing-Wang Wang

Beilstein J. Org. Chem. 2012, 8, 1710–1720, doi:10.3762/bjoc.8.195

• synthesis of pyrazolidine derivatives by Wolfe et al. [33]. In the past decade, the research area of organocatalysis has grown rapidly and become a third brand of catalysis besides the well-established biocatalysis and metal catalysis [34][35][36][37][38][39][40][41][42][43][44]. Particularly

Regio- and stereoselective oxidation of unactivated C–H bonds with Rhodococcus rhodochrous

• Elaine O’Reilly,
• Suzanne J. Aitken,
• Gideon Grogan,
• Paul P. Kelly,
• Nicholas J. Turner and
• Sabine L. Flitsch

Beilstein J. Org. Chem. 2012, 8, 496–500, doi:10.3762/bjoc.8.56

• isomers in yields of up to 26%. Most interestingly, 2-(4-nitrobenzyloxy)tetrahydrofuran and 2-(4-nitrobenzyloxy)tetrahydropyran were transformed in high yields to the 4-hydroxylated and 5-hydroxylated products, respectively. Keywords: biocatalysis; cytochrome P450; hydroxylation; Rhodococcus rhodochrous

Chimeric self-sufficient P450cam-RhFRed biocatalysts with broad substrate scope

• Aélig Robin,
• Valentin Köhler,
• Alison Jones,
• Afruja Ali,
• Paul P. Kelly,
• Elaine O'Reilly,
• Nicholas J. Turner and
• Sabine L. Flitsch

Beilstein J. Org. Chem. 2011, 7, 1494–1498, doi:10.3762/bjoc.7.173

• high-throughput screening protocol for evaluating chimeric, self-sufficient P450 biocatalysts and their mutants against a panel of substrates was developed, leading to the identification of a number of novel biooxidation activities. Keywords: biocatalysis; C–H activation; high-throughput screening

• compounds, GC–MS traces of the biotransformation reactions and the MS traces of the corresponding starting materials. Supporting Information File 196: Experimental part and GC–MS traces. Acknowledgements We wish to thank the Centre of Excellence for Biocatalysis, Biotransformations and Biocatalytic