Abstract
Diels–Alder cycloaddition reaction is one of the most powerful strategies for the construction of six-membered carbocyclic and heterocyclic systems, in most cases with high regio- and stereoselectivity. In this review, an insight into the most relevant advances on sustainable Diels–Alder reactions since 2010 is provided. Various environmentally benign solvent systems are discussed, namely bio-based derived solvents (such as glycerol and gluconic acid), polyethylene glycol, deep eutectic solvents, supercritical carbon dioxide, water and water-based aqueous systems. Issues such as method’s scope, efficiency, selectivity and reaction mechanism, as well as sustainability, advantages and limitations of these reaction media, are addressed.
Highlights
The Diels–Alder reaction, a concerted [4 + 2] cycloaddition of a conjugated diene and a dienophile, is a powerful tool for the regio- and stereoselective construction of six-membered rings [1,2,3,4,5,6]
Driven by the green chemistry principles [8], the demand for sustainable and safe chemical processes over the last two decades has promoted the replacement of volatile organic compounds (VOCs) traditionally used as solvent media in synthetic chemistry with alternative green solvents [9,10,11,12,13,14] or even solvent-free conditions [15]
The second-order rate constant (k2, 7.92 × 10−5 M−1 s−1) determined for the reaction carried at room temperature is about 26-fold higher than that obtained for the same reaction in water
Summary
The Diels–Alder reaction, a concerted [4 + 2] cycloaddition of a conjugated diene and a dienophile, is a powerful tool for the regio- and stereoselective construction of six-membered rings [1,2,3,4,5,6]. Driven by the green chemistry principles [8], the demand for sustainable and safe chemical processes over the last two decades has promoted the replacement of volatile organic compounds (VOCs) traditionally used as solvent media in synthetic chemistry with alternative green solvents [9,10,11,12,13,14] or even solvent-free conditions [15] This endeavor gave rise to the introduction of new solvent media for chemical transformations featuring reduced environmental risk, reduced toxicity, reduced flammability, cost-effectiveness and reusability properties as the major advantages. TThhee tthhrreeee--ccoommppoonneennttazaaz-aD-Dieilesl–sA–Aldledrerrearecaticotnioonf soufbssutibtusttietdutaendilainneisli,naelsd,ehalyddeehsyadneds ealnedcterolenc-trriocnh-arilckhenaelks,eanlesso, kalnsoowknnoaws tnhareset-hcroeme-pcoonmepnot nimenint oim-Dinieol-sD–Aiellds–erArledaecrtiroena,ctoironm, uolrtmicuolmticpoomnepnotnPenotvaProovvarroeavcrtieoanct(iMonC(PMRC),PiRs )o,nise oonf ethoefmthoestmstorsatigsthrtafiogrhwtfaorrdw, aerffidc, ieefnfitcaienndt aatnodma-teocmon-eocmonicoaml sitcraaltsetgriaetsegtoiewsatrodwsacrodms pcolemxpcloerxescostraerstsintagrtfirnogmfrsoimmpsliem, ipnleex, pineenxspiveensainvde aavnadilaabvlaeilmabalteermiaalste. rTiahliss. eTnhviisroennmviernotnamllyenfrtiaelnlydlfyrimenedthlyodmoelothgoydgoilvoegsyacgcievsesstoactceetrsashtyodtertorqahuyindorloinqeusi,nqouliinneosl,inqeusinanoldinjuesloalinddinjeusl,owlidhiinchesa, rwe hscicahffoalrdessocfafgfroeladtsinotfegrerestatininstyenrtehset tiinc osyrgnathneictiacnodrmgaendiicciannadl cmheemdiisctirnyal[4c4h,4e5m].isPteryrin[4a4n,d45c]o. wPeorriknerasnedxpcloowreodrktheersinetxrapmloorleedcutlhaer vinetrrsaimonoolefctuhliasrrveearcstion ofof rthtihserecactatiloynstf-ofrretehseycnatthaleyssist-ofrfeoecstyanhtyhdersoisacorfiodcintaehsysdtarrotaincrgidfrinomes (sRta)r-ctiintrgofnreolmlal(R(1)-)caitnrodnseullbaslt(i1tu) atendd asuryblsatmituinteeds a2ryulsaimngingelsy2ceursoilngasglaycrecroylcalasbalereacnydclaebcloefarniedndelcyos-forliveenndtly(Scshoelvmeen1t )([S4c6h].emCyecl1o)ad[d46u]c.tsC3yacnlodad4dwuecrtes o3btainnded4aswdeiraesteorbetoaiisnoemderaics mdiiaxsttuereos iisnomgoeordictmo hixitguhreysieilndgs o(7o5d–9to8%hi)gahnydiemldosd(e7r5a–te98c%is-)saenledctmivoitdyewrahtencitsh-seerlecatcitviiotny wahsencatrhreierdeaocuttioant 9w0a◦sCc.aCrryiecdlooaudtduatct9s03°/C4. (CRy=cloHa)dwduercetso3b/t4ai(nRed= Hin)lowwereer oybietladin(e6d2%in) uloswinegr wyiaetledr a(6s2s%ol)vuensitn, gwhwearteearsaths esorelvaecntito,nwchaerrieeads othuet irneoacrgtiaonniccasorrliveedntosu(tDiMn SoOrg,aanciectsoonlviternilteso(Dr eMthSaOn,oal)ceatfofonridtreidletohreectohrarneospl)oanfdfoinrdgeaddtdhuecctosrirnesopnolyndtriancgeaadmdouucntstsi.nDounelytotrathce ianmsooluunbtisli.tyDoufe3toanthde4iinnsogluycbeilriotyl, pofro3dauncdts4coinulgdlybceerreoml,opvreoddfurcotms ctohuelrdeabcetiroenmmoevdediumfrobmy dtheecarnetaacttiioonn, amneddtihuemsoblvyendtecaonutladtiboenr,eaunsdedthfoer sfuolrvtheenrt aczoau-Dldieblse–AreludseerdrefaocrtifounrsthweirthaozuatlDoiseslso–fAacldtievritrye.actions without loss of activity
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