Homogeneous Catalysis and Mechanisms in Water and Biphasic Media

160 Pages·2019·18.282 MB·English

by  Luca Gonsalvi

catalysts
Homogeneous
Catalysis and
Mechanisms in
Water and
Biphasic Media
Edited by
Luca Gonsalvi
Printed Edition of the Special Issue Published in Catalysts
www.mdpi.com/journal/catalysts
Homogeneous Catalysis and
Mechanisms in Water and
Biphasic Media

Homogeneous Catalysis and
Mechanisms in Water and
Biphasic Media
SpecialIssueEditor
LucaGonsalvi
MDPI•Basel•Beijing•Wuhan•Barcelona•Belgrade
SpecialIssueEditor
LucaGonsalvi
InstituteofChemistryofOrganometallicCompounds
NationalResearchCouncilofItaly(ICCOM-CNR)
Italy
EditorialOffice
MDPI
St.Alban-Anlage66
4052Basel,Switzerland
ThisisareprintofarticlesfromtheSpecialIssuepublishedonlineintheopenaccessjournalCatalysts
(ISSN2073-4344)from2016to2018(availableat:https://www.mdpi.com/journal/catalysts/special
issues/waterbiphasic)
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Contents
AbouttheSpecialIssueEditor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
LucaGonsalvi
HomogeneousCatalysisandMechanismsinWaterandBiphasicMedia
Reprintedfrom:Catalysts2018,8,543,doi:10.3390/catal8110543 . . . . . . . . . . . . . . . . . . . 1
HuiDong,JieLiu,LifangMaandLiangOuyang
Chitosan Aerogel Catalyzed Asymmetric Aldol Reaction in Water: Highly Enantioselective
Constructionof3-Substituted-3-hydroxy-2-oxindoles
Reprintedfrom:Catalysts2016,6,186,doi:10.3390/catal6120186 . . . . . . . . . . . . . . . . . . . 4
Fre´de´ricHapiotandEricMonflier
Unconventional Approaches Involving Cyclodextrin-Based, Self-Assembly-Driven
ProcessesfortheConversionofOrganicSubstratesinAqueousBiphasicCatalysis
Reprintedfrom:Catalysts2017,7,173,doi:10.3390/catal7060173 . . . . . . . . . . . . . . . . . . . 13
Tuqiao Zhang, Shipeng Chu, Jian Li, Lili Wang, Rong Chen, Yu Shao, Xiaowei Liu and
MiaomiaoYe
Efficient Degradation of Aqueous Carbamazepine by Bismuth Oxybromide-Activated
PeroxideOxidation
Reprintedfrom:Catalysts2017,7,315,doi:10.3390/catal7110315 . . . . . . . . . . . . . . . . . . . 24
JavierFrancosandVictorioCadierno
Metal-CatalyzedIntra-andIntermolecularAdditionofCarboxylicAcidstoAlkynesinAqueous
Media:AReview
Reprintedfrom:Catalysts2017,7,328,doi:10.3390/catal7110328 . . . . . . . . . . . . . . . . . . . 39
VitalyBuckinandMargaridaCarasAltas
UltrasonicMonitoringofBiocatalysisinSolutionsandComplexDispersions
Reprintedfrom:Catalysts2017,7,336,doi:10.3390/catal7110336 . . . . . . . . . . . . . . . . . . . 62
VeraHenricks,IgorYuranov,NordahlAutissierandGa´borLaurenczy
Dehydrogenation of Formic Acid over a Homogeneous Ru-TPPTS Catalyst: Unwanted CO
ProductionandItsSuccessfulRemovalbyPROX
Reprintedfrom:Catalysts2017,7,348,doi:10.3390/catal7110348 . . . . . . . . . . . . . . . . . . . 105
Shu-ichiNakano,MasaoHorita,MikuKobayashiandNaokiSugimoto
CatalyticActivitiesofRibozymesandDNAzymesinWaterandMixedAqueousMedia
Reprintedfrom:Catalysts2017,7,355,doi:10.3390/catal7120355 . . . . . . . . . . . . . . . . . . . 113
YanheYou,JuanLuo,JianweiXieandBinDai
Effect of Iminodiacetic Acid-Modified Nieuwland Catalyst on the Acetylene
DimerizationReaction
Reprintedfrom:Catalysts2017,7,394,doi:10.3390/catal7120394 . . . . . . . . . . . . . . . . . . . 127
AntonellaGuerriero,MaurizioPeruzziniandLucaGonsalvi
Ruthenium(II)-Arene Complexes of the Water-Soluble Ligand CAP as Catalysts for
HomogeneousTransferHydrogenationsinAqueousPhase†
Reprintedfrom:Catalysts2018,8,88,doi:10.3390/catal8020088 . . . . . . . . . . . . . . . . . . . . 138
v

About the Special Issue Editor
LucaGonsalvi(borninParma,Italy,in1968)obtainedhisLaureaDegreeinChemistry(equiv.M.Sc.)
in 1994 at the University of Parma (Italy). From 1996 to 1999, he was a member of the group of
Dr. Anthony Haynes and Prof. Peter M. Maitlis at the University of Sheffield (UK) as Ph. D.
student, with a project on organometallic mechanistic studies on Rh and Ir-catalysed methanol
carbonylation,incollaborationwithBPChemicals. InDecember1999,hemovedtoDelftUniversity
of Technology (NL) as Postdoctoral Research Associate with Prof. Roger A. Sheldon and Prof.
IsabelW.C.E.Arends,developingnewcatalyticapproachestoselectiveetheroxidationtoesters.In
December 2001, he joined ICCOM CNR Florence (Italy) as Staff Researcher, working on water
and biphasic homogeneous catalysis—the synthesis of water-soluble ligands and organometallic
complexes—appliedespeciallytohydrogenandcarbondioxideactivation. Since2010,hehasbeen
SeniorResearcherandGroupLeaderatICCOMCNR.HewasawardedtheUniversityofSheffield
TurnerPrizeforBestPh.D.ChemistryThesis(2000)andtheCNRCareerDevelopmentPrize(2005).
In 2016, he received the Italian National Habilitation as Full Professor in General and Inorganic
Chemistry.Hehasco-authoredmorethan100articlesonpeer-reviewedjournals,filedonepatent,
andpresentedhisworkatmorethan140conferencesandsymposia,includingKeynoteandPlenary
Lectures. He has been Peer Reviewer for 45 scientific journals since 2004. Recently, he has been
ScientificSecretaryofthe28thInternationalConferenceonOrganometallicChemistry(ICOMC2018)
that was held in Florence, Italy, 15–20 July 2018, attended by more than 950 participants from all
continents. Hiscurrentresearchinterests,centredonhomogenouscatalysis,includeorganometallic
chemistryandcatalysisinwater,carbondioxideactivationandutilisation,andhydrogenactivation
bypreciousandearth-abundanttransitionmetals.PersonalWebpage:www.iccom.cnr.it/gonsalvi
vii

catalysts
Editorial
Homogeneous Catalysis and Mechanisms in Water
and Biphasic Media
LucaGonsalvi
InstituteofChemistryofOrganometallicCompounds,NationalResearchCouncilofItaly(ICCOM-CNR),
ViaMadonnadelPiano10,50019SestoFiorentino,Florence,Italy;[email protected]
Received:7November2018;Accepted:12November2018;Published:14November2018
After its discovery in the early 1980s and successful application on an industrial scale
(Ruhrchemie/Rhone-Poulencprocess)[1–4],waterphaseandbiphasiccatalysishavebeenthesubject
offundamentalstudiesinarelativelylimitednumberofresearchlaboratoriesaroundtheworld[5],
almostatacuriositylevel.Duringthelast15years,however,thistopichaswitnessedatruerenaissance,
mainlyduetotheincreasedattentionofindustryandacademiatomoreenvironmentallyfriendly
processes.Wateristhegreensolventparexcellence,andagreatdealofresearchhasbeencarriedoutto
conveythepropertiesofknowntransitionmetalcatalyststotheirwater-solubleanalogs,maintaining
highactivityandselectivity[6]. Thekeystosuccesshavebeen, amongothers, thediscoveryof
syntheticpathwaystonovelmolecularmetal-basedcatalysts[7],newmechanisticinsightsintotherole
ofwaterasanon-innocentsolvent[8],theidentificationofreactionpathwaysthroughexperimental
and theoretical methods, the application of novel concepts for phase transfer agents in biphasic
catalysisandadvancesinengineeringandrelatedtechniquesappliedtovariousreactionscarriedout
inaqueousmedia.
Someoftheapproachescurrentlyusedtotackletheseproblemsaredescribedinthepresent
SpecialIssue,thatcollectsthreereviewarticlesandsixoriginalresearchpapers.Themaincutting-edge
approachesdevelopedinthefieldofaqueousbiphasiccatalysisusingcyclodextrinsasasupramolecular
tool[9]arediscussedandcomparedinthefirstreview[10]. Inthesecondreview[11],thetopic
of the metal-catalyzed addition of carboxylic acids to alkynes [12,13] as a tool for the synthesis
ofcarboxylate-functionalizedolefiniccompoundsisreviewed,withanemphasisonprocessesrun
in water. The synthesis of β-oxo esters by the catalytic addition of carboxylic acids to terminal
propargylicalcoholsinwaterisalsodiscussed.Thethirdreviewarticle[14]describestheuseofan
advancedanalyticalmethod,high-resolutionultrasonicspectroscopy[15],forthenon-destructive
real-timemonitoringofchemicalreactionsincomplexsystemssuchasemulsions,suspensionsand
gels.Thismethodhastheadvantageofbeingapplicabletothemonitoringofreactionsincontinuous
mediaandinmicro/nanobioreactors(e.g.,nanodropletsofmicroemulsions),enablingmeasurements
ofconcentrationsofsubstratesandproductsoverthewholecourseofreaction,evaluationofkinetic
mechanisms,andthemeasurementofkineticandequilibriumconstantsandreactionGibbsenergy.
Tworesearcharticles[16,17]describetheuseofwater-solubleRu(II)complexes[18]forreactions
suchasC=CandC=Nbondtransferhydrogenation[19],andhowtominimizetheproductionofCO
duringHCOOHdehydrogenationreactionsinwatermedia,respectively[20].Otherarticlesdescribe
applicationsinspecialityreactionsandmaterials,forexampletheuseofchitosanaerogel-catalyzed
asymmetricaldolreactionofketoneswithisatinsinthepresenceofwater[21],theuseofbismuth
oxyhalideasanactivatorofperoxideforwaterpurificationtodegradecarbamazepines[22],thestudy
ofcatalyticactivitiesofnucleicacidenzymesindiluteaqueoussolutions[23],theuseofiminodiacetic
acid-modifiedNieuwlandcatalysts[24]foracetylenedimerization,andtheselectiveconversionof
acetylenetomonovinylacetylene(MVA)[25].
Insummary,thisSpecialIssueprovidesanuncommonandmultifocalpointofviewondifferent
fieldsofapplicationwherewatercanbeusedasagreensolventand/orhasimplicationsinthe
Catalysts 2018,8,543;doi:10.3390/catal8110543 1 www.mdpi.com/journal/catalysts