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Synthesis and Properties of Selenium-Containing Sugars and Derivatives

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Synthesis and Properties of Selenium-Containing Sugars and Derivatives pharmaceuticals Review Sweet Selenium: Synthesis and Properties of Selenium-Containing Sugars and Derivatives Francesca Mangiavacchi 1,*, Italo Franco Coelho Dias 1,2, Irene Di Lorenzo 1, Pawel Grzes 3, Martina Palomba 1, Ornelio Rosati 1 , Luana Bagnoli 1 , Francesca Marini 1 , Claudio Santi 1 , Eder Joao Lenardao 2 and Luca Sancineto 1,* 1 Group of Catalysis, Synthesis and Organic Green Chemistry, Department of Pharmaceutical Sciences, University of Perugia, Via del Liceo 1, 06100 Perugia (PG), Italy; [email protected] (I.F.C.D.); [email protected] (I.D.L.); [email protected] (M.P.); [email protected] (O.R.); [email protected] (L.B.); [email protected] (F.M.); [email protected] (C.S.) 2 Laboratory of Clean Organic Synthesis, Federal University of Pelotas, Pelotas 96010-900, Brazil; [email protected] 3 Department of Chemistry, University of Białystok, ul. Ciołkowskiego 1K, 15-245 Białystok, Poland; [email protected] * Correspondence: [email protected] (F.M.); [email protected] (L.S.) Received: 5 August 2020; Accepted: 25 August 2020; Published: 26 August 2020 Abstract: In the last decades, organoselenium compounds gained interest due to their important biological features. However, the lack of solubility, which characterizes most of them, makes their actual clinical exploitability a hard to reach goal. Selenosugars, with their intrinsic polarity, do not suffer from this issue and as a result, they can be conceived as a useful alternative. The aim of this review is to provide basic knowledge of the synthetic aspects of selenosugars, selenonium salts, selenoglycosides, and selenonucleotides. Their biological properties will be briefly detailed. Of course, it will not be a comprehensive dissertation but an analysis of what the authors think is the cream of the crop of this interesting research topic. Keywords: selenium; sugar; selenoglycosides; water-soluble 1. Introduction Organoselenium compounds are gaining interest in the medicinal chemistry community due to their promising biological activities for a wide range of clinical applications [1–7]. Starting from Ebselen, the first compound showing the ability to function as glutathione peroxidase (GPx) mimetic [8], several Se-bearing molecules were reported as anticancer [9–12], anti-inflammatory [13,14], antidepressant [15,16], and antibacterial [17–19], among others. Worth mentioning, some of us developed the DiSeBAs class of compounds [20], endowed with a potent anti-HIV activity due to their ability to inhibit the key viral protein NCp7 [21,22]. In the antiviral research field, Ebselen was recently discovered as the most potent inhibitor of the main protease belonging to the pandemic coronavirus SARS-Cov-2 [23]. The analysis of the physicochemical properties of investigational molecules is a pivotal aspect for scientists involved in designing a pharmacologically active compound. In particular, a certain degree of aqueous solubility is a feature that a compound needs to possess to become bioavailable when administered orally [24,25]. Even if organoselenium compounds do showcase important biological properties, their actual clinical exploitability could be hampered by the low aqueous solubility which precludes them from reaching therapeutically relevant doses in blood. A possible strategy to overcome this barrier is to combine the important pharmacological properties of selenium with the physicochemical properties of sugars, leading to the class of selenosugars and their derivatives, that Pharmaceuticals 2020, 13, 211; doi:10.3390/ph13090211 www.mdpi.com/journal/pharmaceuticals Pharmaceuticals 2020, 13, 211 2 of 28 Pharmaceuticals 2020, 13, 211 22 of of 28 27 with the physicochemical properties of sugars, leading to the class of selenosugars and their withderivatives, the physicochemical that are the object properties of the present of sugars, review leading article. toWith the this class in mind,of selenosugars we aim to reviewand their the derivatives,organoseleniumare the object that of thearecompounds presentthe object review endowed of the article. present with With thereview highest this article. in mind,aqueous With we thissolubility, aim in to mind, review at leastwe the aim from organoselenium to reviewa chemical the organoseleniumpointcompounds of view. endowed Most compounds of with the selenosugars the endowed highest aqueous with developed the solubility, highest to date aqueous at will least be fromsolubility, herein a chemical detailed at least point highlighting from of view.a chemical Mostboth pointtheof the pharmacological of selenosugars view. Most developed ofand the the selenosugars synthetic to date aspects, will developed be herein in or derto detailed date to equip will highlighting bethe herein reader detailed with both useful the highlighting pharmacological knowledge both to theintroduceand pharmacological the synthetic this useful aspects, andbuilding the in ordersynthetic block to in equip aspects,designed the in reader compounds. order with to equip useful the knowledge reader with to useful introduce knowledge this useful to introducebuilding block this useful in designed building compounds. block in designed compounds. 2. Selenopyranes and Selenofuranes 2. Selenopyranes Selenopyranes and and Selenofuranes Selenofuranes One of the first attempts to explore the synthesis of selenocarbohydrates is reported in the works of Schiesser’sOne of the group, firstfirst attempts collected toto exploreinexplore a recently the the synthesis synthesis published of of selenocarbohydrates selenocarbohydratesperspective [26]. Their is is reported reported interest in in thewas the works mainly works of offocusedSchiesser’s Schiesser’s on group,the group, synthesis collected collected of inboth a in recently selenopyranes a recently published published and perspective selenofuranes perspective [26]. as Their [26]. potent interestTheir water-soluble interest was mainly was selenium focusedmainly focusedderivativeson the synthesis on theable synthesis to of act both as selenopyranes potentialof both selenopyranes antioxidants and selenofuranes en anddowed selenofuranes aswith potent good water-solubleas oral potent bioavailability. water-soluble selenium Based derivatives selenium on his derivativesexperienceable to act as onable potential the to seleniumact as antioxidants potential free-radical antioxidants endowed chemistry, with endowed good Schiesser oralwith bioavailability. proposedgood oral thebioavailability. synthesis Based on of his Based 5-seleno-D- experience on his experiencepentopyranoseon the selenium on the protected free-radical selenium sugars chemistry,free-radical 1–7 (Figure Schiesser chemistry, 1), using proposed Schiesser two different the proposed synthesis approaches ofthe 5-seleno-D-pentopyranose synthesis [27]. of 5-seleno-D- pentopyranoseprotected sugars protected1–7 (Figure sugars1), using 1–7 (Figure two di ff1),erent using approaches two different [27]. approaches [27]. Figure 1. Structures of the 5-seleno-pentopyranose. Figure 1. StructuresStructures of of the the 5-seleno-pentopyranose. 5-seleno-pentopyranose. As depicted in Scheme 1, compound 1 was successfully isolated as a mixture of anomers through an intramolecularAs depicted in SchemeSchemehomolytic1 1,, compound compound substitution1 1was was mediat successfully successfullyed by isolated samarium(II)isolated as as a mixturea mixture iodide, of of anomers thatanomers triggers through through the an anformationintramolecular intramolecular of the homolytic radical homolytic intermediate substitution substitution 10 mediated from mediatthe by seleno-aldehyde samarium(II)ed by samarium(II) iodide, 9, which that iodide,was triggers in turnthat the obtained triggers formation from the of formationD-ribosethe radical [27]. of intermediate the radical intermediate10 from the seleno-aldehyde 10 from the seleno-aldehyde9, which was 9 in, which turn obtained was in turn from obtained D-ribose from [27]. D-ribose [27]. OBn OBn OBn OBn BnSeNa D-Ribose MsO BnSe OBn OBn OBn OBnCHO BnSeNa CHO D-Ribose MsO BnSe OBn OBn CHO CHO 8 9 OBn OBn 8 9 SmI2 THF/HMPA SmI2 THF/HMPA OBn OBn (III) BnSe OBn OBn OSm Ln (III) BnSe OBn OSm Ln 10OBn 10 Se OH Se OH BnO OBn BnO OBn OBn 1OBn, 50% 1, 50% Scheme 1. SynthesisSynthesis of of compound compound 11.. Scheme 1. Synthesis of compound 1. Pharmaceuticals 2020, 13, 211 3 of 28 Pharmaceuticals 2020, 13, 211 3 of 27 The same strategy was applied for the synthesis of 2 and 3 starting from D-Xylose and D- Arabinose, respectively. On the other hand, compounds 4–7 were prepared by thermolysis of the Arabinose,The samerespectively. strategy was On appliedthe other for thehand, synthesis compounds of 2 and 43–7starting were fromprepared D-Xylose by thermolysis and D-Arabinose, of the selenoformaterespectively. precursors, On the other in hand, which compounds an intramolecular4–7 were nucleophilic prepared by thermolysisattack of the of benzylselanyl the selenoformate group tookprecursors, place, followed in which by an the intramolecular expulsion of nucleophilic carbon dioxide. attack of Compound the benzylselanyl 4 wasgroup prepared took place,starting followed from D- arabinose,by the expulsion which ofwas carbon converted dioxide. into Compound 2,3,4-tri-4 wasO-benzyl-5- preparedO starting-methanesulfonylarabinose from D-arabinose, which 11was then reduced with NaBH4 and selenofunctionalized through the reaction with benzylselenolate, giving the reducedconverted with into NaBH 2,3,4-tri-4
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