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Recent Advances in Recoverable Systems for the Copper

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Recent Advances in Recoverable Systems for the Copper molecules Review ReviewRecent Advances in Recoverable Systems for the RecentCopper-Catalyzed Advances in Azide-Alkyne Recoverable SystemsCycloaddition for the Copper-CatalyzedReaction (CuAAC) Azide-Alkyne Cycloaddition ReactionAlessandro Mandoli (CuAAC) 1,2 Alessandro1 Dipartimento Mandoli di Chimica1,2 e Chimica Industriale Università di Pisa, Via G. Moruzzi 13, Pisa 56124, Italy; [email protected]; Tel.: +39-050-221-9280 1 Dipartimento di Chimica e Chimica Industriale Università di Pisa, Via G. Moruzzi 13, Pisa 56124, Italy; 2 ISTM-CNR, Via C. Golgi 19, Milano 20133, Italy [email protected]; Tel.: +39-050-221-9280 2AcademicISTM-CNR, Editor: Via Maurizio C. Golgi Benaglia 19, Milano 20133, Italy Received: 1 August 2016; Accepted: 30 August 2016; Published: 3 September 2016 Academic Editor: Maurizio Benaglia Received: 1 August 2016; Accepted: 30 August 2016; Published: 5 September 2016 Abstract: The explosively-growing applications of the Cu-catalyzed Huisgen 1,3-dipolar Abstract:cycloadditionThe reaction explosively-growing between organic azides applications and alkynes of the (CuAAC) Cu-catalyzed have stimulated Huisgen an 1,3-dipolarimpressive cycloadditionnumber of reports, reaction in the between last years, organic focusing azides on and recoverable alkynes (CuAAC) variants haveof the stimulated homogeneous an impressive or quasi- numberhomogeneous of reports, catalysts. in the Recent last years,advances focusing in the onfield recoverable are reviewed, variants with ofparticular the homogeneous emphasis on or quasi-homogeneoussystems immobilized catalysts. onto polymeric Recent advancesorganic or in inorganic the field are supports. reviewed, with particular emphasis on systems immobilized onto polymeric organic or inorganic supports. Keywords: supported catalysts; click-chemistry; continuous-flow chemistry; 1,2,3-triazoles Keywords: supported catalysts; click-chemistry; continuous-flow chemistry; 1,2,3-triazoles 1. Introduction 1. Introduction Efforts towards selectivity, atom economy, generation of molecular diversity, and experimental convenienceEfforts towards have been selectivity, a constant atom drive economy, in modern generation organic ofsynthesis. molecular Still, diversity, their union and in experimental the context convenienceof bond-forming have been(”ligation”) a constant processes, drive in with modern the organicconceptualization synthesis. Still, of ”click-chemistry“ their union in the contextby Kolb, of bond-formingFinn, and Sharpless (”ligation”) [1], appears processes, to have with become the conceptualization a potent trigger of of chemists’ ”click-chemistry“ inventiveness by Kolb, in recent Finn, andyears. Sharpless [1], appears to have become a potent trigger of chemists’ inventiveness in recent years. Essential to this outcome was the parallel and in independentdependent introduction, by the groups of Meldal and Sharpless, of the copper-catalyzed azide-alkyne cycloaddition reaction reaction (Scheme 11))[ [2,3].2,3]. In In fact, the orthogonal character vs. the the reactivity of most functional groups, complete regioselectivity in favor of the 1,4-disustituted-1,2,3-triazole product product 11 (“triazole”(“triazole” hereafter, hereafter, if if not noted otherwise), mild reaction conditions, and easy installation of the required azide and terminal alkyne moieties in the reactive partners, render the metal-promotedmetal-promoted version of the long-standinglong-standing Huisgen 1,3-dipolar cycloaddition reaction the most prominent techniquetechnique inin thethe click-chemistryclick-chemistry toolboxtoolbox [[4,5].4,5]. R1 R1 2 cat. Cu(I) N 1 R 5 N 1 1 2 R N3 + R N + N (base, solvent) 2 N N R 4 12 Scheme 1. The copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC). WithWith applications applications ranging ranging from from material material science science to tomedicinal medicinal chemistry chemistry it is itnot is surprising not surprising that thatinvestigations investigations connected connected with the with CuAAC the CuAACtopic, or ju topic,st making or just use makingof this technique, use of this are technique,appearing arewith appearing impressive with and impressive increasingly and increasinglyhigh frequency high frequencyin the literature. in the literature. As shown As in shown Figure in Figure1, these1, theseadvancements advancements comprise comprise long-standing long-standing topics topics and so andme some incompletely incompletely settled settled aspects aspects like, like,e.g., e.g.,the thereaction reaction mechanism, mechanism, as well as well as asnew new trends trends and and examples examples of of use use of of CuAAC CuAAC in unprecedentedunprecedented directions [[6–61].6–61]. Molecules 2016, 21, 1174; doi:10.3390/molecules21091174 www.mdpi.com/journal/molecules Molecules 2016, 21, 1174; doi:10.3390/molecules21091174 www.mdpi.com/journal/molecules Molecules 2016, 21, 1174 2 of 43 Molecules 2016, 21, 1174 2 of 41 Molecules 2016, 21, 1174 2 of 41 Enzyme modification and Polymer modification and linking [6-10]. Enzymeimmobilization modification [60,61]. and Polymer modification and linking [6-10]. New polymer architectures [11-14]. immobilization [60,61]. NewSynthesis polymer of macrocyclesarchitectures [15,16]. [11-14]. Synthesis of macrocycles [15,16]. Immobilization of small molecules for catalysis [54,55], Immobilizationsensing [56,57], of small chromatography molecules for [58], catalysis and metal [54,55], Smart materials, including stimuli- sensing [56,57], chromatographysorption [59]. [58], and metal Smartresponsive materials, polymers including [17,18] stimuli- and sorption [59]. carbonresponsive nanocomposites polymers [17,18] [19-21]. and carbon nanocomposites [19-21]. Solid-phase and combinatorial Solid-phasechemistry and [52,53].combinatorial Surface modification [22-24] chemistry [52,53]. Surfaceand modification coating [25]. [22-24] Polymerand coating adhesives [25]. [26]. Conjugation and labeling of bio-molecules [43], Polymer adhesives [26]. includingConjugation peptides and labeling [44-46], of polysaccharides bio-molecules [43], [47- including49], peptides and nucleic [44-46], acids polysaccharides [50,51]. [47- New catalytic systems and 49], and nucleic acids [50,51]. reactionNew catalytic mechanism systems [27-30]. and reaction mechanism [27-30]. Synthesis of bio-compatible materials [36-38], drugs,Synthesis and ofother bio-compatible bio-active compounds materials [36-38], [39-42]. drugs, and other bio-active compounds [39-42]. Non-classical CuAAC reaction conditionsNon-classical (e.g. flow CuAAC and reaction microwave Enantioselective CuAAC [34,35]. conditionsactivation (e.g. flow [31-33]). and microwave Enantioselective CuAAC [34,35]. activation [31-33]). FigureFigure 1. 1.Main Main publication publication areas areas ofof CuAAC-relatedCuAAC-related pape papersrs and and selected selected examples examples ofof recent recent trends. trends. Figure 1. Main publication areas of CuAAC-related papers and selected examples of recent trends. InIn addition addition of of being being an an effective effective way way for for linking linking together together different different molecules, molecules, the the appreciation appreciation that In addition of being an effective way for linking together different molecules, the appreciation thethat triazole the structuraltriazole structural motif may motif have may pharmacologic have pharmacologic relevance, e.g.,relevance, as a more e.g., stable as a replacementmore stable for that the triazole structural motif may have pharmacologic relevance, e.g., as a more stable peptidereplacement bonds andfor inpeptide virtue bonds of its dipole and in moment, virtue of hydrogen-bonding, its dipole moment, and hydrogen-bonding,π-π stacking capabilities and π-π [42 ], stackingreplacement capabilities for peptide [42], improvedbonds and further in virtue the ofinterest its dipole towards moment, CuAAC hydrogen-bonding, in the medicinal chemistry and π-π improved further the interest towards CuAAC in the medicinal chemistry field. Even if less represented field.stacking Even capabilities if less represented [42], improved than thefurther isomeric the interest 1,2,4-triazole towards motif, CuAAC contained in the inmedicinal various chemistryapproved than the isomeric 1,2,4-triazole motif, contained in various approved drugs [62,63], examples of drugsfield. Even[62,63], if less examples represented of bio-active than the isomericcompounds 1,2,4-triazole that embed motif, the contained 1,2,3-triazole in various nucleus approved keep bio-active compounds that embed the 1,2,3-triazole nucleus keep appearing continuously in the appearingdrugs [62,63], continuously examples in ofthe bio-active literature orcompounds have already that an establishedembed the clinical1,2,3-triazole use (Figure nucleus 2) [40,42]. keep literatureappearing or havecontinuously already in an the established literature clinicalor have usealready (Figure an established2)[40,42]. clinical use (Figure 2) [40,42]. Figure 2. Selected examples of drugs and other bioactive compounds containing the 1,2,3-triazole nucleus. FigureFigure 2.2. SelectedSelected examples examples of drugs ofand drugsother bioactive and other compounds bioactive containing compounds the 1,2,3-triazole containing nucleus. the 1,2,3-triazole nucleus. Molecules 2016, 21, 1174 3 of 43 MoleculesDespite 2016, the 21, 1174 many successes of CuAAC, the underlying chemistry suffers from three3 of main 41 drawbacks that pose limits to its usefulness, not only in a medicinal
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