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Organocatalysis and Biocatalysis Hand in Hand: Combining Catalysts

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Organocatalysis and Biocatalysis Hand in Hand: Combining Catalysts REVIEWS DOI:10.1002/adsc.201700158 Organocatalysis and Biocatalysis Hand in Hand:Combining Catalysts in One-Pot Procedures Fabricio R. Bisogno,a,*MartínG.López-Vidal,a and Gonzalo de Gonzalob,* a Facultad de CienciasQuímicas,Instituto de Investigaciones en Físico-Química Córdoba(INFIQC-CONICET), Universidad Nacional de Córdoba, 5000 Córdoba, Argentina E-mail:[email protected] b Departamento de QuímicaOrgµnica, Universidad de Sevilla, c/ Profesor GarcíaGonzµlez 1, 41012 Sevilla, Spain E-mail:[email protected] Received:February 8, 2017; Revised:April 5, 2017;Publishedonline:May 11, 2017 DedicatedtoProf.Vicente Gotoronthe occasion of his 70th birthday. Abstract: Multi-stepprocesses catalysed by several 1Introduction catalysts working concurrently have been developed 2Sequential Reactions Employing Organocata- in nature,thusimproving reactionefficiency.The lysts and Biocatalysts quest for novel and improvedcatalytic systems has 3Simultaneous One-Pot ProcessesCombining led to the development of biocatalytic and later to Organocatalysts and Biocatalysts organocatalytic procedures as very valuable tools in 4One-Pot ProcessesCombining Biocatalysts and asymmetric synthesis while using mild reactioncon- Non-TraditionalOrganic Catalysts ditionsinthe absence of metal catalysts.Asatimeless 4.1 Reactions Catalysed by Enzymesand Base Cat- challenge,chemists are facing the need for process alysts designs in which different sorts of catalysts can oper- 4.2 Enzymatic Regeneration of aRedox Catalyst ate successfully in aone-pot concurrentfashion. in aOne-Pot Procedure Likewise,such designs bring about the best of each 4.3 One-Pot Catalytic CombinedRedox Processes catalyst and, in certain cases,enable us to improve Driven by Light problematic issues,such as reactivity,selectivity,solu- 5Outlook bility,inhibition, etc. Specifically, to combine these two types of catalysts in one-pot, achieving high yields and selectivity,isafascinating aspect of cataly- sis.Thisreview covers representativeadvancesin this field, in particular those in which biocatalysts Keywords: concurrent processes;enantioselectivity; and organocatalysts are employed either in sequen- enzyme catalysis;multistep synthesis;one-pot proce- tial reactions or in simultaneous processes. dures;organic catalysis 1Introduction of one reactionisthe substrate of the following one, avoiding intermediate accumulation and, therefore, In nature,the optimisationofagiven process is side reactions.[1] driven by evolutionary pressures.Resource- and Often, chemists employconsecutive multistep energy-savingmaximisation became evolutionary chemical synthesiswith catalytically efficientreactions pressures; hence,cellular machineries,i.e.,enzymatic thus improving the overall“atom economy” of the networks dedicated to aspecificorgeneralcellular process.[2] These methodologies have been widely task, have evolved.Inorder to improvemetabolic ef- adopted in the industrial manufacture of fine chemi- ficiency,living systems make use of several extremely cals and pharmaceutical intermediates.Inthis frame- selectivecatalysts working at the same time,thus work, strategies where multiplecatalysts simultane- forming complex biochemical networks.Toachieve ously work in “one-pot”, avoiding the costly isolation such adegree of success,aperfectregulation of the and purificationofchemical intermediates,are named different catalysts working concomitantly,often in the concurrent.[1a,3] Therefore,reactions taking place in same compartment, became of utmost importance.In the cellular environment are in fact considered as this way, for agiven biosynthetic pathway, the product concurrent. In organic chemistry,ithas been largely Adv.Synth. Catal. 2017, 359,2026 –2049 2026 2017 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim REVIEWS asc.wiley-vch.de Fabricio R. Bisogno obtained Gonzalo de Gonzalo ob- his degree in biochemistry tained his Ph.D.in2003 (2004) at SanLuis National (Prof.Vicente Gotor, Univer- University(Argentina). In sity of Oviedo) working on 2007, he spent half ayear at the field of biocatalysis em- the Weizmann Instituteof ployinglipases andoxynitri- Sciences (Israel, Prof.Meir lases.Hespent his postdoc- Lahav) involved in research toral research at Consiglio on the origin of homochirali- Nazionale delle Ricerche ty.Then, he pursuedPh.D. (ICRM, Milano, Italy,Dr. studies at University of Giacomo Carrea), moving Oviedo (Spain, Prof.Ivµn back to University of Oviedo Lavandera andProf.VicenteGotor), dealing with with aJuan de la Cierva Fellowship.After aone- biocatalytic redox processes(2010). Besides,in2012 year postdoctoral stage at Universityof Groningen he obtained another Ph.D.degree at San Luis Na- (The Netherlands,Prof.Marco W. Fraaije) working tional University(Argentina,Prof.Marcela Kurina- in the research of noveloxidative biocatalysts,he Sanz) working on fungal biotransformation of bioac- spent two years at the R&D Department of the tive compounds. After postdocperiods in Oviedo pharmaceutical company Antibióticos S.A.U.(León, and Córdoba(Argentina), in 2013 he joined Prof Spain). He is currently aRamónand Cajal Re- Alicia PeÇØÇorysgroup as researcher at Córdoba searcher (MINECO) at UniversityofSevilla. His re- National Universityand INFIQC-CONICET (Ar- search is focused on asymmetric synthesis by using gentina).His research interest comprisescombina- different approaches,including biocatalytic andor- tion of biocatalysis with metal catalysisand organo- ganocatalytic procedures, as wellasthe development catalysisfor the constructionofcooperativesystems, of concurrent chemo- and biocatalytic reactions. along with exploration of novel reactivities for organo-sulfur-and organo-selenium-containingcom- pounds in enzymatic or biomimetic processes. MartínG.López-Vidal ob- tained his degree in biochem- istry at Córdoba National University(2014, Argentina). In 2015, he joined Prof Alicia PeÇØÇorysgroup as aPh.D. CONICET-fellow,under the guidance of Fabricio R. Bi- sogno at Córdoba National University. In 2016 he spent athree-months stay in the Laboratory of Biocatalysis at the UniversityofGraz (Austria) exploringthe reactivity of sulfur-contain- ing compoundswith ene-reductases under the super- vision of Prof MØlanie Hall. His researchinterest is focused on the development of novel chemoenzy- matic cascades for stereoselective preparation of or- ganochalcogen-compounds. demonstrated that running multiplereactions in one- agents are addedatthe beginning, thus requiring only pot, either in sequential (also known as stepwise, one operational step) mode,ischallenging to agreat when operationssuch as addition of catalysts/re- extent given the diverging reactionconditions suitable agents,temperature/atmosphere modification, etc. are for each single transformation.[4] Thus,tremendous ef- made during the course of the process to ensure the forts are made in order to find proper conditions to proper reactivity mode) or simultaneous (also known harmonically combine multiple catalytic reactions as cascade or domino reactions,inwhich conditions with no cross-spoiling effects.[5] are not modified during the process and catalysts/re- Adv.Synth. Catal. 2017, 359,2026 –2049 2027 2017 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim REVIEWS asc.wiley-vch.de In abroad sense,organocatalysis can be definedas the acceleration of achemical reactionusing an or- 2SequentialReactions Employing ganic compound in substoichiometric amounts in the Organocatalystsand Biocatalysts absence of (transition) metals.[6] On the other hand, an acceptable definition of biocatalysis in organic syn- Initially,weshall deal with processes in which the or- thesis can be the employment of abiomolecule (pro- ganocatalyst andthe biocatalyst are able to catalyse tein, antibody,ribozyme) or aliving organism to carry sequential reactions in order to have multistep one- out the transformation of a(non-)natural organic pot procedures(Figure 1).[12] Theselectivity of the compound.[7] final productswhen chiral compounds are synthes- Nowadays,bothorganocatalysis and biocatalysis ised, can be induced by only the organocatalyst,by are becoming mature and amechanistic understand- only the biocatalyst or by both catalysts performing ing of enzymatic reactions alongwith catalytically- selectivereactions in the sequential process. productive organic associations have been deeply in- vestigated. It is rather remarkable that the number of examples where both sorts of catalysis working con- currently were successfully applied is limitedwhen comparedwith the far more explored combination of metal catalysed processesand biocatalysis.[8] Some re- ports have been published based on the combination of transition metals and organocatalysts;[9] but not so many examples are availabledealing with the combi- nation of organocatalysis andbiocatalysis in one-pot procedures.[10] It must be takeninto account that organic substan- ces are not always soluble in aqueous media, so aproper solvent selection is usually an issue in both Figure1.Schematic representation of asequential one-pot organo- and biocatalytic systems.Notwithstanding, process using organocatalysis and biocatalysis. the use of cosolvents or additives (in the frame of a“medium engineering” concept), is acommon prac- tice in those catalytic methodologies,thus circumvent- One of the first examples described in the literature ing solubility and, in certain cases,reactivity prob- of asequential multistep one-pot process combining lems.[11] Foracombination of organo- andbiocatalytic organocatalystsand enzymes, was published in 2004
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