Functionalised diimidazolium salts: The anion effect on the catalytic ability

Article abstract of DOI:10.1039/c6ra12037g

The catalytic ability of some functionalised diimidazolium ionic liquids was tested using the Michael addition of malononitrile to t-chalcone as probe reaction. Diimidazolium salts characterized by the presence of 1-(1-imidazolylmethyl)-3,5-di-[1-(3-octylimidazolylmethyl)]benzene cation and differing in the anion structure were used. Both mono- and dianions were employed and among these some chiral anions generally used as organocatalysts were taken into account. Data collected were analysed both as function of ionic liquids structure and basicity, evaluated using the Hammett basicity function. Although the use of chiral anions did not allow performing a stereochemical control of the reaction, data collected demonstrate the high catalytic ability of the functionalised salts. Indeed, high conversions and yields were obtained under mild conditions and in significantly shorter reaction times with respect to the ones so far reported for this reaction.

Full text of DOI:10.1039/c6ra12037g

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Page 1 of 11
Please Rꢀ d So Cꢀ n oA t dꢀ av da j nu cs teꢀ ms arginsꢀ
View Article Online
DOI: 10.1039/C6RA12037G
JournalꢀNameꢀ
ꢀ
ARTICLEꢀ
Functionalisedꢀdiimidazoliumꢀsalts:ꢀtheꢀanionꢀeffectꢀonꢀtheꢀ
catalyticꢀabilityꢀꢀꢀ
Receivedꢀ00thꢀJanuaryꢀ20xx,ꢀ
Acceptedꢀ00thꢀJanuaryꢀ20xxꢀ
a
a
ꢀaꢀ
CarlaꢀRizzo, ꢀFrancescaꢀD’Anna *ꢀandꢀRenatoꢀNoto
DOI:ꢀ10.1039/x0xx00000xꢀ
Theꢀ catalyticꢀ abilityꢀ ofꢀ someꢀ functionalisedꢀ diimidazoliumꢀ ionicꢀ liquidsꢀ wasꢀ testedꢀ usingꢀ theꢀ Michaelꢀ additionꢀ ofꢀ
malononitrileꢀ toꢀ t-chalconeꢀ asꢀ probeꢀ reaction.ꢀ Diimidazoliumꢀ saltsꢀ characterizedꢀ byꢀ theꢀ presenceꢀ ofꢀ 1-(1-
imidazolylmethyl)-3,5-di-[1-(3-octylimidazolylmethyl)]benzeneꢀcationꢀandꢀdifferingꢀinꢀtheꢀanionꢀstructureꢀwereꢀused.ꢀBothꢀ
mono-ꢀandꢀdianionsꢀwereꢀemployedꢀandꢀamongꢀtheseꢀsomeꢀchiralꢀanionsꢀgenerallyꢀusedꢀasꢀorganocatalystsꢀwereꢀtakenꢀ
intoꢀaccount.ꢀDataꢀcollectedꢀwereꢀanalysedꢀbothꢀasꢀfunctionꢀofꢀionicꢀliquidsꢀstructureꢀandꢀbasicity,ꢀevaluatedꢀusingꢀtheꢀ
Hammettꢀbasicityꢀfunction.ꢀAlthoughꢀtheꢀuseꢀofꢀchiralꢀanionsꢀdidꢀnotꢀallowꢀperformingꢀaꢀstereochemicalꢀcontrolꢀofꢀtheꢀ
reaction,ꢀdataꢀcollectedꢀdemonstrateꢀtheꢀhighꢀcatalyticꢀabilityꢀofꢀtheꢀfunctionalisedꢀsalts.ꢀIndeed,ꢀhighꢀconversionsꢀandꢀ
yieldsꢀ wereꢀ obtainedꢀ underꢀ mildꢀ conditionsꢀ andꢀ inꢀ significantlyꢀ shorterꢀ reactionꢀ timesꢀ withꢀ respectꢀ toꢀ theꢀ onesꢀ soꢀ farꢀ
reportedꢀforꢀthisꢀreaction.ꢀ
www.rsc.org/ꢀ
ofꢀTSILsꢀhaveꢀbeenꢀconsidered.ꢀAsꢀforꢀimidazolium-basedꢀILs,ꢀ
nitrile-functionalisedꢀ ILsꢀ haveꢀ beenꢀ exploitedꢀ toꢀ coordinateꢀ
metalsꢀactiveꢀinꢀcatalysisꢀlikeꢀpalladium.ꢀTheseꢀTSILsꢀhaveꢀbeenꢀ
usedꢀbothꢀasꢀsolventsꢀandꢀstabilizersꢀinꢀpalladiumꢀcatalysedꢀC-Cꢀ
Introductionꢀ
Theꢀ choiceꢀ ofꢀ solventꢀ andꢀ catalystꢀ isꢀ crucial,ꢀ tuningꢀ upꢀ newꢀ
syntheticꢀ proceduresꢀ orꢀ inꢀ theꢀ attemptꢀ toꢀ improveꢀ reactionꢀ
conditions.ꢀAsꢀfarꢀasꢀsolventsꢀareꢀconcerned,ꢀinꢀtheꢀlastꢀfifteenꢀ
6,ꢀ 7
cross-couplingꢀ reactions. ꢀ Onꢀ theꢀ otherꢀ hand,ꢀ aꢀ primaryꢀ
amino-functionalisedꢀ imidazoliumꢀ ILꢀ hasꢀ beenꢀ usedꢀ inꢀ
8
1
,ꢀ 2 [bmim][PF6]ꢀasꢀligandꢀandꢀbaseꢀforꢀtheꢀHeckꢀreaction. ꢀ
years,ꢀ ionicꢀ liquidsꢀ (ILs)ꢀ haveꢀ playedꢀ aꢀ significantꢀ role.
Thanksꢀ toꢀ theirꢀ lowꢀ vapourꢀ pressureꢀ andꢀ flammability,ꢀ theyꢀ
haveꢀ beenꢀ consideredꢀ asꢀ efficientꢀ optionsꢀ toꢀ conventionalꢀ
organicꢀsolventsꢀ(COSs).ꢀAfterꢀtheirꢀfirstꢀuseꢀasꢀsolventꢀmedia,ꢀ
alsoꢀtheꢀpossibilityꢀofꢀincorporatingꢀfunctionalꢀgroupsꢀintoꢀtheꢀ
cationꢀ orꢀ anionꢀ hasꢀ beenꢀ takenꢀ intoꢀ account.ꢀ Thisꢀ allowsꢀ
obtainingꢀfunctionalisedꢀILsꢀgenerallyꢀnamedꢀ“taskꢀspecificꢀILs”ꢀ
ꢀ
AsꢀforꢀTSILsꢀbearingꢀtheꢀactiveꢀfunctionꢀonꢀtheꢀanionꢀstructure,ꢀ
someꢀyearsꢀagoꢀweꢀpreparedꢀtheꢀ1-butyl-3-methylimidazoliumꢀ
azideꢀandꢀweꢀusedꢀitꢀasꢀaꢀsourceꢀofꢀnucleophile,ꢀinꢀILꢀsolution,ꢀ
toꢀ promoteꢀ arylꢀ azideꢀ formationꢀ fromꢀ correspondingꢀ arylꢀ
9,ꢀ10
halides. ꢀꢀꢀ
Inꢀtheꢀlastꢀdecade,ꢀtheꢀfurtherꢀevolutionꢀofꢀILsꢀclassꢀhasꢀbeenꢀ
11
representedꢀ byꢀ di-ꢀ andꢀ polycationicꢀ ones. ꢀ Withꢀ respectꢀ toꢀ
monocationicꢀILs,ꢀtheyꢀshowꢀhigherꢀthermalꢀstabilityꢀandꢀlowerꢀ
miscibilityꢀwithꢀconventionalꢀorganicꢀsolventsꢀ(COSs).ꢀRecently,ꢀ
theꢀ opportunityꢀ toꢀ anchorꢀ aꢀ catalyticꢀ functionalityꢀ onꢀ theꢀ
cationꢀ orꢀ anionꢀ structureꢀ toꢀ obtainꢀ functionalisedꢀ di-ꢀ orꢀ
polycationicꢀ ILsꢀ hasꢀ beenꢀ evaluatedꢀ (TSDILsꢀ andꢀ TSPILs,ꢀ
respectively).ꢀ So,ꢀ acidicꢀ TSDILsꢀ haveꢀ beenꢀ usedꢀ forꢀ biomassꢀ
(
TSILs).ꢀTheyꢀwereꢀfirstlyꢀdefinedꢀbyꢀDavisꢀinꢀ2004ꢀasꢀorganicꢀ
saltsꢀ ableꢀ toꢀ behaveꢀ notꢀ onlyꢀ asꢀ reactionꢀ media,ꢀ butꢀ alsoꢀ toꢀ
exertꢀ specificꢀ actionꢀ thanksꢀ toꢀ theꢀ presenceꢀ ofꢀ aꢀ functionalꢀ
3
groupꢀtetheredꢀtoꢀtheꢀcationꢀand/orꢀanion. ꢀTSILsꢀhaveꢀbeenꢀ
alsoꢀdesignedꢀtoꢀremoveꢀchemicallyꢀtoxicꢀandꢀradiotoxicꢀmetalꢀ
4
ionsꢀ fromꢀ aqueousꢀ media. ꢀ Theyꢀ haveꢀ beenꢀ frequentlyꢀ
consideredꢀ “rivals”ꢀ ofꢀ solidꢀ supportedꢀ catalysts,ꢀ asꢀ theyꢀ
increaseꢀ theꢀ kineticꢀ mobilityꢀ andꢀ allowꢀ aꢀ largeꢀ operationalꢀ
surfaceꢀ area.ꢀ Furthermore,ꢀ theꢀ incorporationꢀ ofꢀ functionalꢀ
groupsꢀinꢀtheꢀILꢀstructureꢀminimizesꢀtheꢀleakageꢀofꢀtheꢀcatalystꢀ
andꢀcanꢀincreaseꢀtheꢀrecyclabilityꢀofꢀtheꢀsolvent-catalystꢀmediaꢀ
forꢀ severalꢀ catalyticꢀ cycles.ꢀ Literatureꢀ aboutꢀ TSILsꢀ hasꢀ beenꢀ
12,ꢀ 13
transformationꢀ inꢀ productsꢀ ofꢀ industrialꢀ value.
ꢀ Onꢀ theꢀ
otherꢀhand,ꢀaꢀradicalꢀfunctionalityꢀhasꢀbeenꢀalsoꢀtetheredꢀonꢀ
someꢀdiimidazoliumꢀILsꢀandꢀusedꢀinꢀtheꢀoxidationꢀofꢀprimaryꢀ
14
andꢀsecondaryꢀalcohols. ꢀ
Inꢀthisꢀcontext,ꢀasꢀaꢀdevelopmentꢀofꢀourꢀworkꢀaimedꢀtoꢀstudyꢀ
1
5,ꢀ 16
5
ILsꢀ propertiesꢀ andꢀ applications,
ꢀ twoꢀ yearsꢀ agoꢀ weꢀ
synthesizedꢀsomeꢀTSDILsꢀcharacterizedꢀbyꢀtheꢀpresenceꢀofꢀ1-
1-imidazolylmethyl)-3,5-di-[1-(3-
octylimidazolylmethyl)]benzeneꢀ ([2C8bti ])ꢀ cationꢀ andꢀ havingꢀ
comprehensivelyꢀreviewedꢀbyꢀChiappeꢀetꢀal.. ꢀDifferentꢀkindsꢀ
(
2+
17
differentꢀ mono-ꢀ andꢀ dianions. ꢀ Theꢀ presenceꢀ ofꢀ aꢀ neutralꢀ
imidazoleꢀunitꢀonꢀtheꢀcationꢀstructureꢀmadeꢀtheseꢀTSDILsꢀveryꢀ
efficientꢀ reactionꢀ mediaꢀ forꢀ theꢀ baseꢀ catalysedꢀ mononuclearꢀ
rearrangementꢀ ofꢀ heterocyclesꢀ (MHR)ꢀ reaction.ꢀ Theyꢀ actedꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ1ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Please Rꢀ d So Cꢀ n oA t dꢀ av da j nu cs teꢀ ms arginsꢀ
Page 2 of 11
ARTICLEꢀ
JournalꢀNameꢀ
bothꢀ asꢀ solventsꢀ andꢀ catalystsꢀ allowingꢀ theꢀ obtainmentꢀ ofꢀ inꢀtheꢀpresenceꢀofꢀTSDILs.ꢀDILsꢀareꢀfrequentlyꢀclaimVieewdAꢀrftioclreꢀOthnleinierꢀ
DOI: 10.1039/C6RA12037G
triazolesꢀ withꢀ highꢀ yieldsꢀ andꢀ theꢀ recycleꢀ ofꢀ theꢀ solvent- abilityꢀ toꢀ induceꢀ effectsꢀ markedlyꢀ differentꢀ fromꢀ theꢀ onesꢀ
1
8
28-30
catalystꢀ system. ꢀ Amongꢀ anionsꢀ used,ꢀ adipateꢀ ([ad])ꢀ andꢀ observedꢀ inꢀ simpleꢀ monocationicꢀ ILs.
suberateꢀ ([sub])ꢀ wereꢀ theꢀ onesꢀ ableꢀ toꢀ awardꢀ theꢀ highestꢀ hasꢀ raisedꢀ someꢀ questions:ꢀ i)ꢀ canꢀ theꢀ useꢀ ofꢀ TSDILsꢀ beꢀ
catalyticꢀabilityꢀtoꢀsolventꢀsystems.ꢀ advantageousꢀ inꢀ termsꢀ ofꢀ reactionꢀ time?ꢀ ii)ꢀ What’sꢀ theꢀ roleꢀ
ꢀ Consequently,ꢀ thisꢀ
Inꢀ theꢀ lightꢀ ofꢀ theꢀ aboveꢀ results,ꢀ weꢀ thoughtꢀ itꢀ couldꢀ beꢀ playedꢀbyꢀtheꢀcatalystꢀtetheredꢀtoꢀtheꢀionicꢀstructure?ꢀiii)ꢀIsꢀtheꢀ
interestingꢀ toꢀ testꢀ someꢀ ofꢀ theꢀ aboveꢀ TSDILsꢀ andꢀ someꢀ newꢀ anionꢀ anꢀ “inert”ꢀ viewerꢀ orꢀ doesꢀ itꢀ playꢀ aꢀ role?ꢀ iv)ꢀ Canꢀ theꢀ
diimidazoliumꢀ saltsꢀ (fromꢀ nowꢀ onꢀ theyꢀ willꢀ beꢀ referredꢀ asꢀ combinationꢀofꢀaꢀbaseꢀfunctionalisedꢀcationꢀwithꢀchiralꢀanionsꢀ
functionalisedꢀdicationicꢀorganicꢀsalts,ꢀTSDILs)ꢀforꢀtheꢀstudyꢀofꢀ affectꢀtheꢀstereochemicalꢀpathway?ꢀ
Michaelꢀadditionꢀofꢀmalononitrileꢀtoꢀt-chalconeꢀ(Schemeꢀ1).ꢀAsꢀ Toꢀanswerꢀtheseꢀquestions,ꢀweꢀsynthesizedꢀsomeꢀTSDILsꢀbasedꢀ
2+
-
probeꢀreaction,ꢀitꢀcouldꢀbeꢀofꢀaꢀcertainꢀinterestꢀas,ꢀotherwiseꢀ onꢀ [2C8bti ]ꢀ cationꢀ endowedꢀ withꢀ bothꢀ mono-ꢀ ([Br ])ꢀ andꢀ
theꢀ MHRꢀ reaction,ꢀ thisꢀ isꢀ aꢀ bimolecularꢀ reactionꢀ andꢀ couldꢀ dianionsꢀ (Schemeꢀ 1).ꢀ Chiralꢀ carboxylatesꢀ andꢀ phosphateꢀ
allowꢀ sheddingꢀ lightꢀ onꢀ differentꢀ factorsꢀ affectingꢀ catalyticꢀ anions,ꢀ suchꢀ asꢀ L-prolinateꢀ ([L-pro]),ꢀ L-phenylalaninateꢀ ([L-
abilityꢀofꢀtheꢀusedꢀTSDILs.ꢀFurthermore,ꢀgivingꢀriseꢀtoꢀaꢀchiralꢀ phe])ꢀ andꢀ (R)-(-)-1,1’-binaphthyl-2,2’-diylꢀ phosphateꢀ ([R-
product,ꢀ itꢀ couldꢀ allowꢀ evaluatingꢀ alsoꢀ theꢀ “chiralꢀ inductionꢀ BNphosph])ꢀwereꢀused.ꢀInꢀparticular,ꢀ[L-pro]ꢀandꢀ[L-phe]ꢀwereꢀ
solvent”.ꢀThisꢀbaseꢀcatalysedꢀreactionꢀisꢀofꢀgreatꢀsignificanceꢀasꢀ usedꢀ asꢀ theꢀ correspondingꢀ aminoacidsꢀ areꢀ amongꢀ theꢀ mostꢀ
3
1-36
itꢀrepresentsꢀaꢀusefulꢀsyntheticꢀstrategyꢀforꢀtheꢀobtainmentꢀofꢀ widelyꢀ employedꢀ organocatalysts.
intermediateꢀnitrilesꢀableꢀtoꢀgiveꢀ4-oxobutanamides,ꢀwhichꢀareꢀ theꢀ lastꢀ fewꢀ years,ꢀ differentꢀ papersꢀ haveꢀ claimedꢀ theꢀ chiralꢀ
ꢀ Onꢀ theꢀ otherꢀ hand,ꢀ inꢀ
22,ꢀ 37
foundꢀinꢀaꢀlotꢀofꢀnaturalꢀandꢀunnaturalꢀcompoundsꢀdisplayingꢀ inductionꢀ ofꢀ binaphthylꢀ phosphates.
ꢀ Asꢀ forꢀ dianions,ꢀ
19
bothꢀpharmacologicalꢀandꢀbiologicalꢀproperties. ꢀTheꢀMichaelꢀ togetherꢀ withꢀ [ad]ꢀ andꢀ [sub]ꢀ usedꢀ forꢀ goodꢀ performancesꢀ
additionꢀhasꢀbeenꢀinvestigatedꢀinꢀCOSs,ꢀbothꢀasꢀaꢀfunctionꢀofꢀ showedꢀinꢀMHRꢀreaction,ꢀalsoꢀchiralꢀdicarboxylates,ꢀsuchꢀasꢀL-ꢀ
20,ꢀ 21
solventꢀandꢀbase. ꢀFurthermore,ꢀinꢀtheꢀpresenceꢀofꢀchiralꢀ andꢀD-tartrateꢀ([tar]),ꢀwereꢀconsidered.ꢀꢀ
catalystsꢀsuchꢀasꢀCinchonaꢀalkaloidsꢀandꢀquinidineꢀderivatives,ꢀ Finally,ꢀtoꢀevaluateꢀtheꢀrelevanceꢀofꢀtheꢀbaseꢀcatalystꢀonꢀtheꢀ
goodꢀ chemicalꢀ yieldsꢀ withꢀ highꢀ levelsꢀ ofꢀ diastereo-ꢀ andꢀ dicationꢀ structure,ꢀ theꢀ Michaelꢀ additionꢀ wasꢀ alsoꢀ performedꢀ
2
2,ꢀ23
enantioselectivitiesꢀhaveꢀbeenꢀdetected.
ꢀꢀ
usingꢀ
theꢀ
3,3’-di-N-octyl-1,1’-(1,3-
dibromideꢀ ([m-
C8im][Br]2)ꢀasꢀsolventꢀsystemꢀandꢀ1-methylimidazoleꢀasꢀbasicꢀ
Michaelꢀ additionꢀ hasꢀ beenꢀ alsoꢀ studiedꢀ inꢀ monocationicꢀ ILsꢀ phenylenedimethylene)diimidazoliumꢀ
24-27ꢀ
solutionꢀ eitherꢀ inꢀ theꢀ presenceꢀ orꢀ withoutꢀ catalyst.
However,ꢀtoꢀtheꢀbestꢀofꢀourꢀknowledge,ꢀnoꢀdataꢀhaveꢀbeenꢀsoꢀ catalyst.ꢀ
farꢀreportedꢀaboutꢀtheꢀstudyꢀofꢀthisꢀreactionꢀinꢀDILsꢀorꢀbetterꢀ
ꢀ
Reaction studied:
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
NC
CN
O
O
NC
+
NC
1
2
3
ILs used:
N
N
N
2
Br
N
N
/ Y2
2
X
8 17
C H
N
N
N
C8H17
C8H17
N
N
C8H17
[
2C8bti][X]2 or [2C8bti][Y]
[m-C8im][Br]2
COO
COO
H
COO
NH2
O
O
O
H
OH
H
HO
H
H
P
(
CH2)4
(CH2)6
COO
X = Br
N
H
O
OOC
COO
OOC
COO
HO
OH
COO
COO
[
L-pro]
[L-phe]
[R- BNphosph]
Y = [ad]
Y = [sub]
Y = [L-tar]
Y = [D-tar]
Schemeꢀ1.ꢀRepresentationꢀofꢀtheꢀreactionꢀstudiedꢀandꢀTSDILsꢀused.ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
2
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 3 of 11
Please Rꢀ d So Cꢀ n oA t dꢀ av da j nu cs teꢀ ms arginsꢀ
JournalꢀNameꢀ
ꢀARTICLEꢀ
ResultsꢀandꢀDiscussionꢀ
lessꢀ greenꢀ reactionꢀ conditionsꢀ (Tableꢀ 1,ꢀ entryꢀ 5V)i.eꢀwTAhrteicꢀleloOwnlienerꢀ
DOI: 10.1039/C6RA12037G
catalyticꢀ efficiencyꢀ ofꢀ 1-methylimidazole,ꢀ withꢀ respectꢀ toꢀ
K2CO3,ꢀ isꢀ perfectlyꢀ ascribableꢀ toꢀ itsꢀ lowerꢀ basicityꢀ (Tableꢀ 1,ꢀ
entriesꢀ1-2).ꢀꢀ
Inꢀorderꢀtoꢀapplyꢀtheꢀbestꢀreactionꢀconditions,ꢀweꢀfirstꢀperformedꢀ
theꢀ Michaelꢀ additionꢀ inꢀ aꢀ conventionalꢀ solvent,ꢀ tetrahydrofuranꢀ
Onꢀ theꢀ groundsꢀ ofꢀ theseꢀ results,ꢀ weꢀ subsequentlyꢀ studiedꢀ
TSDILꢀeffectsꢀperformingꢀreactionsꢀatꢀ25ꢀ°Cꢀandꢀusingꢀaꢀsmallꢀ
excessꢀ ofꢀ theꢀ methyleneꢀ activeꢀ compoundꢀ (t-
chalcone/malononitrileꢀ1:ꢀ1.3;ꢀTablesꢀ2-3ꢀandꢀ5).ꢀ
38
(
THF)ꢀasꢀthisꢀisꢀoneꢀofꢀtheꢀsolventsꢀmostꢀcommonlyꢀused. ꢀIndeed,ꢀ
theꢀ reactionꢀ isꢀ notꢀ favouredꢀ inꢀ highlyꢀ polarꢀ solvents.ꢀ Itꢀ hasꢀ beenꢀ
claimedꢀthatꢀsolvents,ꢀlikeꢀDMFꢀandꢀDMSO,ꢀunderꢀbasicꢀconditions,ꢀ
favourꢀtheꢀconversionꢀofꢀdicyanideꢀ(3)ꢀinꢀtheꢀmonocyanideꢀproductꢀ
ItꢀisꢀworthꢀofꢀrememberingꢀthatꢀsomeꢀofꢀourꢀTSDILsꢀatꢀ25ꢀ°Cꢀ
wereꢀ waxyꢀ solidꢀ andꢀ theirꢀ consistencyꢀ madeꢀ difficultꢀ theꢀ
evaluationꢀ ofꢀ volume.ꢀ Consequently,ꢀ weꢀ performedꢀ ourꢀ
investigationꢀkeepingꢀconstantꢀtheꢀTSDIL/substrateꢀmolarꢀratioꢀ
(1;ꢀ≈ꢀ0.15ꢀmmol),ꢀandꢀthisꢀwasꢀsmallerꢀthanꢀtheꢀoneꢀusedꢀforꢀ
(
4)ꢀ throughꢀ anꢀ aerobicꢀ oxidationꢀ andꢀ aꢀ subsequentꢀ eliminationꢀ
20
reactionꢀ(Chartꢀ1). ꢀꢀ
O
CN
18
theꢀMHRꢀreactionꢀ(4.5). ꢀFurthermore,ꢀamongꢀsaltsꢀused,ꢀonlyꢀ
2C8bti][R-BNphosph]2ꢀhadꢀaꢀmeltingꢀpointꢀhigherꢀthanꢀ100ꢀ°Cꢀ
seeꢀ Experimental)ꢀ andꢀ cannotꢀ beꢀ exactlyꢀ definedꢀ aꢀ TSDIL.ꢀ
[
ꢀ
4
(
ꢀ
2
0
Chartꢀ1.ꢀMonocyanideꢀderivingꢀfromꢀdicyanideꢀ(3). ꢀ
However,ꢀ weꢀ decidedꢀ toꢀ useꢀ itꢀ toꢀ testꢀ itsꢀ “chiralꢀ inductionꢀ
ability”ꢀonꢀtheꢀprobeꢀreaction.ꢀ
ꢀ
18
Onꢀtheꢀotherꢀhand,ꢀitꢀisꢀwellꢀknownꢀthatꢀinorganic,ꢀlikeꢀK2CO3ꢀ HavingꢀinꢀmindꢀtheꢀresultsꢀobtainedꢀinꢀtheꢀMHRꢀreaction, ꢀweꢀ
21
orꢀKOH,ꢀcatalyseꢀtheꢀreaction. ꢀꢀ
firstlyꢀ usedꢀ TSDILsꢀ presentingꢀ theꢀ bestꢀ catalyticꢀ ability,ꢀ i.e.ꢀ
Weꢀ tookꢀ inꢀ considerationꢀ aꢀ weakerꢀ organicꢀ baseꢀ suchꢀ asꢀ 1- [2C8bti][sub]ꢀ andꢀ [2C8bti][ad].ꢀ Tableꢀ 2ꢀ summarizesꢀ resultsꢀ
methylimidazole,ꢀasꢀitꢀrepresentsꢀtheꢀbasicꢀfunctionalityꢀofꢀtheꢀ obtainedꢀ inꢀ termsꢀ ofꢀ percentageꢀ conversionꢀ ofꢀ t-chalconeꢀ asꢀ
TSDILsꢀused.ꢀ
functionꢀofꢀamountꢀandꢀnatureꢀofꢀcosolvent.ꢀꢀ
Obviously,ꢀotherꢀimportantꢀexperimentalꢀparameters,ꢀlikeꢀtheꢀ Theꢀ[ad]-basedꢀTSDILꢀwasꢀemployedꢀasꢀreferenceꢀsolvent,ꢀandꢀ
ratioꢀbetweenꢀt-chalconeꢀandꢀmalononitrile,ꢀtheꢀtemperatureꢀ weꢀ performedꢀ theꢀ firstꢀ investigationꢀ atꢀ 25ꢀ °C.ꢀ However,ꢀ asꢀ
andꢀ timeꢀ ofꢀ reactionꢀ wereꢀ evaluatedꢀ (Tableꢀ 1).ꢀ Forꢀ aꢀ usefulꢀ aboveꢀstated,ꢀatꢀroomꢀtemperatureꢀourꢀTSDILsꢀwereꢀsolidꢀlikeꢀ
comparison,ꢀ dataꢀ previouslyꢀ collectedꢀ inꢀ THFꢀ usingꢀ K2CO3ꢀ asꢀ orꢀ waxyꢀ solids.ꢀ Consequently,ꢀ theꢀ reactionꢀ requiredꢀ longꢀ
20
baseꢀareꢀalsoꢀreported. ꢀInꢀallꢀcases,ꢀweꢀusedꢀtheꢀcatalystꢀinꢀ reactionꢀtimeꢀandꢀtheꢀuseꢀofꢀultrasoundꢀirradiationꢀtoꢀgiveꢀ72%ꢀ
stoichiometricꢀamountꢀwithꢀrespectꢀtoꢀt-chalconeꢀandꢀtheꢀfinalꢀ yieldꢀ(Tableꢀ2,ꢀentryꢀ1).ꢀꢀ
productꢀwasꢀisolatedꢀbyꢀflashꢀchromatography.ꢀꢀ
ꢀ
Inꢀ orderꢀ toꢀ improveꢀ theꢀ reactionꢀ conditionsꢀ andꢀ lowerꢀ theꢀ
energeticꢀdemandꢀofꢀtheꢀprocess,ꢀweꢀperformedꢀtheꢀreactionꢀ
Tableꢀ 1.ꢀ Reactionꢀ conditionsꢀ appliedꢀ forꢀ theꢀ studyꢀ ofꢀ Michaelꢀ inꢀ theꢀ presenceꢀ ofꢀ aꢀ cosolvent.ꢀ Thisꢀ shouldꢀ decreaseꢀ theꢀ
aꢀ
additionꢀofꢀmalononitrileꢀtoꢀt-chalconeꢀinꢀTHF.
systemꢀviscosityꢀfavouringꢀtheꢀcontactꢀbetweenꢀtheꢀreagents.ꢀ
Atꢀ aꢀ firstꢀ sight,ꢀ MeOHꢀ appearedꢀ toꢀ beꢀ aꢀ suitableꢀ choice.ꢀ
ꢀ
ꢀ
Moleꢀ
Entryꢀ
Timeꢀ Yieldꢀ
Indeed,ꢀourꢀTSDILsꢀwereꢀreallyꢀsolubleꢀinꢀthisꢀsolventꢀandꢀitsꢀ
ratioꢀ
Catalystꢀ
Tꢀ(°C)ꢀ
(
h)ꢀ
(3)ꢀ
(
useꢀcouldꢀavoidꢀtheꢀpresenceꢀofꢀdifferentꢀmicrodomainsꢀinꢀtheꢀ
1
/2ꢀ
bꢀ
%)
c
solventꢀ system,ꢀ exertingꢀ differentꢀ effectsꢀ onꢀ theꢀ outcomeꢀ ofꢀ
1
2
3
4
5
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
1:ꢀ1.1ꢀ
1:1.3ꢀ
1:1.3ꢀ
1:1.3ꢀ
1:10ꢀ
K
2
CO
3
ꢀ
25ꢀꢀ
25ꢀꢀ
25ꢀ&ꢀUSꢀ
40ꢀꢀ
12ꢀ
16ꢀꢀ
1ꢀꢀ
94 ꢀ
0ꢀ
1-methylimidazoleꢀ
1-methylimidazoleꢀ
1-methylimidazoleꢀ
1-methylimidazoleꢀ
theꢀ reaction.ꢀ Then,ꢀ weꢀ searchedꢀ forꢀ theꢀ smallestꢀ cosolventꢀ
volumeꢀ and,ꢀ fixingꢀ theꢀ reactionꢀ timeꢀ atꢀ 30ꢀ minutes,ꢀ weꢀ
12ꢀ
41ꢀ
43ꢀ
1ꢀ
performedꢀ investigationꢀ graduallyꢀ increasingꢀ theꢀ MeOHꢀ
volumeꢀ(Tableꢀ2,ꢀentriesꢀ2-4).ꢀ
25ꢀꢀ
22ꢀ
a
b
Reactionsꢀ wereꢀ performedꢀ usingꢀ 1ꢀ mLꢀ ofꢀ THF.ꢀ Yieldsꢀ wereꢀ
reproducibleꢀwithinꢀ4%.ꢀProductꢀisolatedꢀbyꢀflashꢀchromatography.ꢀ
Fromꢀref.ꢀ20.
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
c
ꢀ
ꢀ
ꢀ
Dataꢀ collectedꢀ showꢀ that,ꢀ inꢀ ourꢀ experimentalꢀ conditions,ꢀ 1-
methylimidazoleꢀwasꢀnotꢀableꢀtoꢀcatalyseꢀtheꢀreactionꢀatꢀ25ꢀ°Cꢀ
(
Tableꢀ 1,ꢀ entryꢀ 2).ꢀ Onꢀ theꢀ otherꢀ hand,ꢀ keepingꢀ constantꢀ t-
chalcone/malononitrileꢀratioꢀtoꢀ1/1.3,ꢀitꢀwasꢀnecessaryꢀtoꢀuseꢀ
ultrasoundꢀ irradiationꢀ orꢀ aꢀ temperatureꢀ ofꢀ 40ꢀ °Cꢀ toꢀ obtainꢀ aꢀ
lowꢀorꢀmoderateꢀyieldꢀinꢀaꢀshortꢀreactionꢀtimeꢀ(1ꢀh)ꢀ(Tableꢀ1,ꢀ
entryꢀ 3-4).ꢀ ꢀ Evenꢀ thoughꢀ onlyꢀ 12ꢀ %ꢀ andꢀ 41ꢀ %ꢀ yieldsꢀ wereꢀ
respectivelyꢀ obtained,ꢀ furtherꢀ increasingꢀ theꢀ temperatureꢀ
causedꢀtheꢀformationꢀofꢀsomeꢀby-products.ꢀOnꢀtheꢀotherꢀhand,ꢀ
maintainingꢀ theꢀ temperatureꢀ atꢀ 25ꢀ °C,ꢀ theꢀ increaseꢀ ofꢀ t-
chalcone/malononitrileꢀmoleꢀratioꢀfromꢀ1:1.3ꢀtoꢀ1:10ꢀbroughtꢀ
toꢀaꢀhigherꢀyieldꢀbutꢀwithꢀaꢀlongꢀreactionꢀtimeꢀ(22ꢀh)ꢀandꢀusingꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ3ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Please Rꢀ d So Cꢀ n oA t dꢀ av da j nu cs teꢀ ms arginsꢀ
Page 4 of 11
ARTICLEꢀ
JournalꢀNameꢀ
Tableꢀ 2.ꢀ Percentageꢀ conversionꢀ forꢀ theꢀ Michaelꢀ additionꢀ ofꢀ
malononitrileꢀtoꢀt-chalconeꢀperformedꢀatꢀ25ꢀ°Cꢀinꢀtheꢀpresenceꢀofꢀ
theꢀ oneꢀ previouslyꢀ reportedꢀ byꢀ Tomaꢀ etꢀ al.ꢀ studyingꢀ theꢀ
View Article Online
27DOI: 10.1039/C6RA12037G
Michaelꢀ additionꢀ inꢀ monocationicꢀ ILs. ꢀ Onꢀ theꢀ otherꢀ hand,ꢀ
[
8
2C bti][ad]ꢀ asꢀ aꢀ functionꢀ ofꢀ cosolventꢀ volume,ꢀ andꢀ inꢀ theꢀ
someꢀ yearsꢀ ago,ꢀ performingꢀ baseꢀ catalysedꢀ reactionsꢀ inꢀ
monocationicꢀILs,ꢀweꢀalsoꢀevidencedꢀaꢀhigherꢀcatalyticꢀabilityꢀ
ofꢀaliphaticꢀaminesꢀwithꢀrespectꢀtoꢀtheꢀoneꢀdetectedꢀinꢀCOSsꢀ
8
presenceꢀofꢀ[2C bti][sub]ꢀasꢀaꢀfunctionꢀofꢀcosolventꢀnature.ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
8
[2C bti][ad]ꢀ
a,b
Entryꢀ
MeOHꢀ
reactionꢀ
timesꢀ
Conversion
ꢀ
andꢀ weꢀ ascribedꢀ theꢀ effectꢀ observedꢀ toꢀ theꢀ lessꢀ extensiveꢀ
39,ꢀ40
(
µL)ꢀ
0ꢀ
solvationꢀofꢀreagentsꢀoperatingꢀinꢀILꢀsolution.
ꢀTheseꢀeffectsꢀ
c
1
2
3
4
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
3.25ꢀh ꢀ
72%ꢀ
85%ꢀ
83%ꢀ
>95%ꢀ
couldꢀoperateꢀalsoꢀinꢀthisꢀcaseꢀgivingꢀriseꢀtoꢀresultsꢀcollected.ꢀ
Then,ꢀweꢀtestedꢀtheꢀreactionꢀinꢀtheꢀpresenceꢀofꢀ[2C8bti][sub],ꢀ
usingꢀtheꢀsameꢀconditionsꢀ(25ꢀ°C,ꢀ30ꢀmin,ꢀ60ꢀµLꢀofꢀMeOH)ꢀandꢀ
weꢀobtainedꢀaꢀ74%ꢀconversionꢀofꢀsubstrateꢀ(Tableꢀ2,ꢀentryꢀ10).ꢀ
Asꢀsecondꢀstage,ꢀweꢀbecameꢀinterestedꢀwhetherꢀitꢀisꢀfeasibleꢀ
toꢀanalyseꢀtheꢀeffectꢀofꢀcosolventꢀnature.ꢀIndeed,ꢀsomeꢀyearsꢀ
agoꢀ performingꢀ theꢀ MHRꢀ reactionꢀ inꢀ IL/COSꢀ binaryꢀ mixtures,ꢀ
weꢀdemonstratedꢀthatꢀtheꢀrateꢀofꢀtheꢀaboveꢀreactionꢀchangedꢀ
asꢀaꢀfunctionꢀofꢀcosolventꢀnatureꢀandꢀmostꢀsignificantꢀeffectsꢀ
couldꢀbeꢀdetectedꢀwhenꢀsmallꢀvolumesꢀofꢀCOSꢀwereꢀaddedꢀtoꢀ
20ꢀ
40ꢀ
60ꢀ
0.5ꢀhꢀ
0.5ꢀhꢀ
0.5ꢀhꢀ
8
[2C bti][sub]ꢀ
a
ꢀ
cosolventꢀ
1,4-
ε
Conversion ꢀ
b
5
ꢀ
2.21ꢀ
73% ꢀ
dioxaneꢀ
tolueneꢀ
d
6
7
8
9
ꢀ
ꢀ
ꢀ
ꢀ
2.40ꢀ
4.81ꢀ
7.58ꢀ
20.1ꢀ
32.7ꢀ
36.7ꢀ
>95% ꢀ
d
CHCl
3
ꢀ
89% ꢀ
d
THFꢀ
92% ꢀ
41
d
IL. ꢀToꢀpursueꢀtheꢀaboveꢀaim,ꢀweꢀdecidedꢀtoꢀuseꢀ[2C8bti][sub]ꢀ
1-PrOHꢀ
MeOHꢀ
DMFꢀ
90% ꢀ
b
asꢀ TSDILꢀ becauseꢀ conversionꢀ ofꢀ t-chalconeꢀ wasꢀ notꢀ
quantitativeꢀ andꢀ betterꢀ thanꢀ [2C8bti][ad]ꢀ itꢀ couldꢀ allowꢀ
evaluatingꢀtheꢀroleꢀplayedꢀbyꢀtheꢀcosolventꢀnatureꢀ(Tableꢀ2).ꢀꢀ
Weꢀ alwaysꢀ usedꢀ 60ꢀ µLꢀ ofꢀ cosolventꢀ andꢀ conversionsꢀ rangedꢀ
fromꢀ 73%ꢀ inꢀ theꢀ presenceꢀ ofꢀ 1,4-dioxaneꢀ toꢀ 95%ꢀ inꢀ theꢀ
presenceꢀofꢀtolueneꢀorꢀDMF.ꢀTheꢀconversionꢀofꢀtheꢀsubstrateꢀisꢀ
highꢀ usingꢀ cosolventsꢀ ofꢀ lowꢀ orꢀ mediumꢀ polarityꢀ suchꢀ asꢀ
toluene,ꢀ chloroform,ꢀ THFꢀ andꢀ 1-propanol.ꢀ However,ꢀ inꢀ theseꢀ
cases,ꢀ itꢀ isꢀ comprehensiveꢀ ofꢀ theꢀ presenceꢀ ofꢀ someꢀ by-
products,ꢀ whichꢀ couldꢀ notꢀ beꢀ easilyꢀ separatedꢀ fromꢀ theꢀ
productꢀ desiredꢀ andꢀ identified.ꢀ Differently,ꢀ 1,4-dioxane,ꢀ
MeOH,ꢀDMFꢀandꢀACNꢀonlyꢀgiveꢀtheꢀdesiredꢀproduct.ꢀ
1
1
0ꢀ
1ꢀ
74% ꢀ
b
>95% ꢀ
a
Conversionꢀ obtainedꢀ atꢀ 25ꢀ °C.ꢀ Conversionsꢀ wereꢀ reproducibleꢀ
withinꢀ4%.ꢀProductꢀisolatedꢀbyꢀflashꢀchromatography;ꢀ conversionsꢀ
b
ꢀ
c
andꢀ yieldsꢀ wereꢀ almostꢀ coincident; reactionꢀ performedꢀ atꢀ roomꢀ
d
temperatureꢀassistedꢀbyꢀultrasoundꢀirradiation;ꢀ formationꢀofꢀby-
products.ꢀ
ꢀ
InꢀtheꢀpresenceꢀofꢀaꢀreallyꢀlowꢀMeOHꢀvolumeꢀ(60ꢀµLꢀ-ꢀmolarꢀ
ratioꢀ substrate/TSDIL/MeOH=1/1/1),ꢀ weꢀ obtainedꢀ anꢀ almostꢀ
quantitativeꢀ substrateꢀ conversionꢀ andꢀ thisꢀ definitelyꢀ inducedꢀ
usꢀtoꢀavoidꢀtheꢀuseꢀofꢀenergyꢀsourceꢀinꢀneatꢀTSDILꢀasꢀitꢀdidꢀnotꢀ
induceꢀimprovementsꢀbothꢀinꢀtermsꢀofꢀyieldꢀandꢀreactionꢀtime.ꢀ
Itꢀisꢀnoteworthyꢀthat,ꢀdifferentlyꢀfromꢀdataꢀcollectedꢀinꢀTHF,ꢀinꢀ
theꢀ presenceꢀ ofꢀ [2C8bti][ad],ꢀ weꢀ detectedꢀ aꢀ significantꢀ
conversionꢀofꢀt-chalconeꢀinꢀspiteꢀofꢀtheꢀshortꢀreactionꢀtimeꢀ(30ꢀ
min).ꢀClearly,ꢀthisꢀpointsꢀoutꢀaꢀpositiveꢀeffectꢀofꢀtheꢀusedꢀTSDIL.ꢀ
Theꢀ resultꢀ obtainedꢀ couldꢀ beꢀ ascribedꢀ toꢀ aꢀ higherꢀ acidityꢀ ofꢀ
methyleneꢀ compoundꢀ inꢀ thisꢀ medium,ꢀ asꢀ wellꢀ asꢀ toꢀ aꢀ
significantꢀincreaseꢀinꢀbasicityꢀofꢀneutralꢀimidazoleꢀunitꢀborneꢀ
Consideringꢀ theꢀ aboveꢀ results,ꢀ weꢀ decidedꢀ toꢀ useꢀ MeOHꢀ asꢀ
cosolventꢀ asꢀ itꢀ gaveꢀ riseꢀ toꢀ aꢀ goodꢀ conversionꢀ allowingꢀ
investigatingꢀTDSILsꢀeffectsꢀ(seeꢀlater)ꢀbetterꢀthanꢀDMFꢀorꢀACNꢀ
thatꢀpresentedꢀtheꢀalmostꢀtotalꢀconversionꢀofꢀtheꢀsubstrateꢀinꢀ
theꢀdesiredꢀproduct.ꢀ
Theꢀ furtherꢀ stepꢀ ofꢀ ourꢀ investigationꢀ wasꢀ theꢀ studyꢀ ofꢀ theꢀ
influenceꢀ ofꢀ TSDILsꢀ anionsꢀ onꢀ theꢀ Michaelꢀ addition,ꢀ
determiningꢀreactionꢀtimesꢀandꢀpercentageꢀyieldsꢀ(Tableꢀ3).ꢀ
ꢀ
2+
onꢀtheꢀ[2C8bti ]ꢀcation.ꢀTheꢀfirstꢀhypothesisꢀwellꢀagreesꢀwithꢀ
ꢀ
Tableꢀ3.ꢀPercentageꢀyieldsꢀofꢀproductsꢀ(3)ꢀandꢀ(4)ꢀandꢀconversionsꢀforꢀtheꢀMichaelꢀadditionꢀperformedꢀinꢀtheꢀpresenceꢀofꢀTSDILsꢀatꢀ25ꢀ
aꢀ
°
C.
ꢀ
b
b
b
Entryꢀ
TSDILꢀ
Reactionꢀ
time ꢀ(h)ꢀ
Yieldꢀ%(3) ꢀ
Yieldꢀ%(4) ꢀ
Conversionꢀ% ꢀ
b
1
ꢀ
ꢀ
[m-C
[2C bti][Br]
[2C bti][ad]ꢀ
[2C
[2C
8
im][Br]
2
ꢀ
24ꢀ
74ꢀ
93ꢀ
0ꢀ
0ꢀ
78ꢀ
2
8
2
ꢀ
5.5ꢀ
>95ꢀ
3
4
ꢀ
ꢀ
8
0.5ꢀ
0.5ꢀ
>95ꢀ
74ꢀ
0ꢀ
0ꢀ
>95ꢀ
78ꢀ
8
bti][sub]ꢀ
5
ꢀ
8
bti][D-tar]ꢀ
24ꢀ
47ꢀ
20ꢀ
67ꢀ
6
7
8
9
ꢀ
ꢀ
ꢀ
ꢀ
[2C
[2C
[2C
bti][R-BNphosph]
8
bti][L-tar]ꢀ
bti][L-pro]
bti][L-phe]
24ꢀ
0.15ꢀ
0.5ꢀ
24ꢀ
47ꢀ
63ꢀ
56ꢀ
24ꢀ
25ꢀ
35ꢀ
0ꢀ
71ꢀ
92ꢀ
91ꢀ
83ꢀ
8
2
ꢀ
8
2
ꢀ
[2C
8
2
ꢀ
78ꢀ
a
ꢀ
b
Reactions wereꢀ performedꢀ usingꢀ aꢀ 1/1/1ꢀ substrate/TSDIL/MeOHꢀ molarꢀ ratio. Yieldsꢀ andꢀ conversionsꢀ wereꢀ reproducibleꢀ withinꢀ 4%.ꢀ
Productsꢀwereꢀisolatedꢀbyꢀflashꢀchromatography.ꢀ
4
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 5 of 11
Please Rꢀ d So Cꢀ n oA t dꢀ av da j nu cs teꢀ ms arginsꢀ
JournalꢀNameꢀ
ꢀARTICLEꢀ
ꢀ
View Article Online
Tableꢀ4.ꢀH
ofꢀHammettꢀindicator.ꢀ
-
ꢀvaluesꢀdeterminedꢀforꢀTSDILsꢀatꢀ
DOI: 0 /C6RA120 G
25ꢀ° C1 0ꢀ u. 1s i n3 9g ꢀtheꢀmet h3 7o dꢀ
Firstly,ꢀ toꢀ evaluateꢀ theꢀ relevanceꢀ ofꢀ theꢀ useꢀ ofꢀ TSDILs,ꢀ weꢀ
carriedꢀ outꢀ theꢀ reactionꢀ usingꢀ theꢀ unfunctionalisedꢀ DIL,ꢀ [m-
C8im][Br]2,ꢀinꢀtheꢀpresenceꢀofꢀ1-methylimidazoleꢀinꢀequimolarꢀ
amountꢀꢀtoꢀDILꢀandꢀt-chalcone.ꢀAfterꢀ24ꢀh,ꢀweꢀobtainedꢀaꢀ74ꢀ%ꢀ
yieldꢀ (Tableꢀ 3,ꢀ entryꢀ 1).ꢀ Onꢀ goingꢀ fromꢀ [m-C8im][Br]2ꢀ toꢀ
a
b
BromocresolꢀGreen ꢀ
p-nitrophenol ꢀ
c
c
TSDILsꢀ
H
-
ꢀ
TSDILsꢀ
_
H ꢀ
[
2C8bti][Br]2,ꢀ weꢀ observedꢀ aꢀ significantꢀ decreaseꢀ inꢀ reactionꢀ
[2C bti][tar]ꢀ
9.6ꢀ
[2C bti][L-pro] ꢀ
11.8ꢀ
8
8
2
timeꢀandꢀaꢀgoodꢀimprovementꢀinꢀyieldꢀ(Tableꢀ3,ꢀentriesꢀ1-2),ꢀ
evidencingꢀtheꢀadvantageꢀofꢀusingꢀTSDILsꢀandꢀsupportingꢀtheꢀ
importanceꢀofꢀtheꢀcatalystꢀdirectlyꢀlinkedꢀtoꢀtheꢀILꢀcation.ꢀ
Then,ꢀweꢀperformedꢀtheꢀreactionꢀinꢀtheꢀpresenceꢀofꢀallꢀTSDILs.ꢀ
Reactionꢀtimesꢀrangeꢀfromꢀ10ꢀminꢀupꢀtoꢀ24ꢀh.ꢀInꢀgeneral,ꢀtheyꢀ
representꢀaꢀgreatꢀchallengeꢀwithꢀrespectꢀtoꢀtheꢀonesꢀpreviouslyꢀ
d
[
2C
8
bti][Br]
2
ꢀ
9.3 ꢀ
[2C
8
bti][L-phe]
2
ꢀ
10.9ꢀ
d
[2C bti][R-BNphosh] ꢀ
8
2
8.6ꢀ
ꢀ
[2C bti][ad]ꢀ
8
10.7 ꢀ
d
ꢀ
[2C
8
bti][sub]ꢀ
10.5 ꢀ
a
b
c
_
pKaꢀ (MeOH)ꢀ =ꢀ 9.80.ꢀ pKaꢀ (MeOH)ꢀ =ꢀ 11.30.ꢀ H ꢀ valuesꢀ wereꢀ
d
reportedꢀinꢀCOSsꢀasꢀwellꢀasꢀinꢀILꢀsolution.ꢀIndeed,ꢀinꢀtheꢀfirstꢀ reproducibleꢀwithinꢀ±ꢀ0.1.ꢀ FromꢀRef.ꢀ18.ꢀ
case,ꢀatꢀroomꢀtemperature,ꢀreactionꢀtimesꢀrangingꢀfromꢀ12ꢀupꢀ
toꢀ100ꢀhꢀareꢀreported.
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
1
,8
,6
,4
,2
0
42,ꢀ43
1,5
(b)
bromocresol green
[2C8bti][binaphtilphosph]2
[2C8bti][L-tar]2
ꢀOnꢀtheꢀotherꢀhand,ꢀasꢀaboveꢀstated,ꢀ
(a)
p-nitrophenol
[
[
2C8bti][L-phenylalaninate]2
2C8bti][L-prolinate]2
0
0
0
0
theꢀMichaelꢀadditionꢀhasꢀbeenꢀperformedꢀinꢀmonocationicꢀILs.ꢀ
Althoughꢀreactionꢀtimesꢀgoingꢀfromꢀ30ꢀsecꢀupꢀtoꢀ3ꢀhꢀhaveꢀbeenꢀ
reportedꢀforꢀthiolsꢀadditionꢀtoꢀt-chalcone,ꢀwhenꢀmalononitrileꢀ
wasꢀ usedꢀ asꢀ nucleophile,ꢀ reactionꢀ timesꢀ ofꢀ 2ꢀ orꢀ 22ꢀ hꢀ wereꢀ
detectedꢀ asꢀ piperidineꢀ orꢀ L-prolineꢀ wereꢀ theꢀ basicꢀ catalysts,ꢀ
respectively.ꢀ Furthermore,ꢀ theꢀ before-mentionedꢀ reactions,ꢀ
wereꢀperformedꢀusingꢀhigherꢀIL/substrateꢀmoleꢀratioꢀthanꢀtheꢀ
1
0
,5
0
350
400
450
500
550
600
650
700
2
50
300
350
400
450
500
26,ꢀ 27
λ (nm)
oneꢀusedꢀbyꢀusꢀ(ꢀ~ꢀ5ꢀandꢀ1ꢀforꢀmonocationic
ꢀandꢀTSDILs,ꢀ
λ (nm)
respectively).ꢀThisꢀfurtherꢀshedsꢀlightꢀonꢀtheꢀcatalyticꢀabilityꢀofꢀ
saltsꢀusedꢀinꢀthisꢀwork.ꢀ
Figureꢀ1.ꢀUV-visꢀspectraꢀofꢀ(a)ꢀp-nitrophenolꢀandꢀ(b)ꢀbromocresolꢀ
greenꢀcollectedꢀinꢀMeOHꢀandꢀatꢀaꢀfixedꢀconcentrationꢀofꢀTSDIL.ꢀ
AmongꢀTSDILs,ꢀtheꢀMichaelꢀadditionꢀselectivelyꢀproceededꢀinꢀ
theꢀ presenceꢀ ofꢀ [2C8bti][Br]2,ꢀ [2C8bti][R-BNphosph]2,ꢀ
ꢀ
Amongꢀ TSDILsꢀ used,ꢀ theꢀ lowestꢀ basicityꢀ wasꢀ detectedꢀ forꢀ
[
reactionꢀmediaꢀforꢀtheꢀtargetꢀreaction,ꢀperfectlyꢀrecallingꢀwhatꢀ
2C8bti][ad]ꢀ andꢀ [2C8bti][sub].ꢀ Theꢀ latterꢀ twoꢀ areꢀ theꢀ bestꢀ
[
2C8bti][R-BNphosph]2ꢀ whereasꢀ theꢀ highestꢀ wasꢀ theꢀ oneꢀ
correspondingꢀtoꢀ[2C8bti][L-pro]2.ꢀObviously,ꢀinꢀtheꢀlatterꢀcaseꢀ
asꢀ wellꢀ asꢀ inꢀ theꢀ caseꢀ ofꢀ [2C8bti][L-phe]2),ꢀ aꢀ contributionꢀ toꢀ
18
weꢀpreviouslyꢀobservedꢀstudyingꢀtheꢀMHRꢀreaction. ꢀꢀ
Inꢀ allꢀ theꢀ otherꢀ casesꢀ ([2C8bti][tar],ꢀ [2C8bti][L-pro]2ꢀ andꢀ
(
basicityꢀcanꢀalsoꢀbeꢀdueꢀtoꢀtheꢀpresenceꢀofꢀaminoꢀgroupꢀinꢀtheꢀ
anion.ꢀ Theꢀ aboveꢀ twoꢀ TSDILsꢀ wereꢀ theꢀ onesꢀ inꢀ whichꢀ theꢀ
highestꢀandꢀlowestꢀreactionꢀtimesꢀwereꢀdetected,ꢀrespectively.ꢀ
OnꢀtheꢀgroundsꢀofꢀH-ꢀvalues,ꢀbasicityꢀofꢀTSDILsꢀincreasesꢀalongꢀ
theꢀseries:ꢀ[2C8bti][R-BNphosph]2ꢀ<ꢀ[2C8bti][Br]2ꢀ<ꢀ[2C8bti][tar]ꢀ
[
2C8bti][L-phe]2),ꢀweꢀdetectedꢀtheꢀpresenceꢀofꢀtwoꢀproductsꢀinꢀ
theꢀreactionꢀmixture.ꢀAfterꢀseparationꢀbyꢀchromatographyꢀandꢀ
characterizationꢀ byꢀ meansꢀ ofꢀ NMRꢀ andꢀ GC-MSꢀ investigation,ꢀ
weꢀidentifiedꢀbothꢀdi-(3)ꢀandꢀmonocyanideꢀ(4).ꢀHowever,ꢀwhileꢀ
inꢀtheꢀcaseꢀofꢀ[2C8bti][tar],ꢀmoderateꢀyieldsꢀwereꢀobtainedꢀinꢀaꢀ
longꢀ reactionꢀ timeꢀ (Tableꢀ 3,ꢀ entriesꢀ 5-6),ꢀ aminoacids-basedꢀ
TSDILsꢀwereꢀableꢀtoꢀgiveꢀfastlyꢀmoderateꢀyieldsꢀinꢀtheꢀproductꢀ
desired.ꢀ
<ꢀ [2C8bti][sub]ꢀ <ꢀ [2C8bti][ad]ꢀ <ꢀ [2C8bti][L-phe]2ꢀ <ꢀ [2C8bti][L-
pro]2.ꢀTheꢀaboveꢀtrendꢀcanꢀnotꢀexplainꢀdifferencesꢀinꢀreactionꢀ
times.ꢀIndeed,ꢀitꢀdoesꢀnotꢀjustifyꢀtheꢀonesꢀbetweenꢀ[tar]-ꢀandꢀ
[
Br]-basedꢀ TSDILs.ꢀ Furthermore,ꢀ H-ꢀ valuesꢀ doꢀ notꢀ allowꢀ
justifyingꢀ theꢀ almostꢀ quantitativeꢀ conversionꢀ detectedꢀ inꢀ theꢀ
presenceꢀofꢀbothꢀ[2C8bti][ad]ꢀandꢀ[2C8bti][sub].ꢀ
Takingꢀ intoꢀ accountꢀ theꢀ baseꢀ catalysisꢀ operatingꢀ onꢀ theꢀ
reaction,ꢀandꢀtoꢀhaveꢀaꢀfurtherꢀsupportꢀtoꢀexplainꢀtheꢀaboveꢀ
experimentalꢀtrend,ꢀweꢀdeterminedꢀtheꢀbasicityꢀfunctionꢀ(H-),ꢀ
forꢀ theꢀ newꢀ chiralꢀ TSDILsꢀ inꢀ MeOHꢀ solution,ꢀ usingꢀ theꢀ
Hammettꢀmethod.ꢀThisꢀcolorimetricꢀmethodꢀhasꢀbeenꢀappliedꢀ
byꢀ usꢀ andꢀ others,ꢀ toꢀ assessꢀ theꢀ basicityꢀ ofꢀ functionalisedꢀ
Inꢀ general,ꢀ theꢀ increaseꢀ inꢀ basicityꢀ favoursꢀ theꢀ substrateꢀ
conversion.ꢀ However,ꢀ higherꢀ basicityꢀ ([L-phe]ꢀ andꢀ [L-pro]ꢀ
anions)ꢀ orꢀ longerꢀ reactionꢀ timeꢀ ([tar]ꢀ anions)ꢀ speedꢀ upꢀ theꢀ
furtherꢀ transformationꢀ ofꢀ dicyanideꢀ (3)ꢀ inꢀ monocyanideꢀ (4)ꢀ
inducingꢀaꢀdropꢀinꢀtheꢀselectivityꢀofꢀtheꢀreaction.ꢀ
18,ꢀ 44
dicationicꢀ ILs.
ꢀ Weꢀ areꢀ awareꢀ ofꢀ theꢀ factꢀ thatꢀ situationꢀ
detectedꢀ inꢀ MeOHꢀ solutionꢀ couldꢀ beꢀ differentꢀ fromꢀ theꢀ oneꢀ
occurringꢀinꢀtheꢀreactionꢀmixtures.ꢀHowever,ꢀtheꢀevaluationꢀofꢀ
H-ꢀ functionꢀ couldꢀ giveꢀ generalꢀ informationꢀ aboutꢀ TSDILsꢀ
basicity.ꢀꢀ
Takingꢀ inꢀ considerationꢀ theꢀ aboveꢀ results,ꢀ weꢀ fixedꢀ theꢀ
reactionꢀtimeꢀatꢀ30ꢀminꢀtoꢀhaveꢀaꢀbetterꢀcomparisonꢀamongꢀ
catalyticꢀabilityꢀofꢀTDSILsꢀ(Tableꢀ5).ꢀꢀ
Consideringꢀproductꢀ(3),ꢀtheꢀpercentageꢀyieldsꢀobtainedꢀwereꢀ
higherꢀinꢀnon-chiralꢀTSDILs,ꢀtheꢀhighestꢀvaluesꢀwereꢀdetectedꢀ
inꢀ[2C8bti][ad]ꢀandꢀ[2C8bti][sub]ꢀTSDILs.ꢀTheꢀtrendꢀobservedꢀasꢀ
functionꢀ ofꢀ differentꢀ TSDILsꢀ anionsꢀ isꢀ theꢀ followingꢀ one:ꢀ
Basicityꢀshowedꢀsignificantꢀchangesꢀasꢀaꢀfunctionꢀofꢀtheꢀnatureꢀ
ofꢀtheꢀanion.ꢀThisꢀisꢀtheꢀreasonꢀwhyꢀbothꢀbromocresolꢀgreenꢀ
andꢀp-nitrophenolꢀwereꢀusedꢀasꢀsolvatochromicꢀprobes.ꢀDataꢀ
collectedꢀareꢀreportedꢀinꢀTableꢀ4;ꢀwhereasꢀUV-visꢀspectraꢀareꢀ
displayedꢀinꢀFigureꢀ1.ꢀ
[
2C8bti][L-pro]2ꢀ <ꢀ [2C8bti][R-BNphosph]2ꢀ <ꢀ [2C8bti][D-tar]ꢀ ≈ꢀ
ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ5ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Please Rꢀ d So Cꢀ n oA t dꢀ av da j nu cs teꢀ ms arginsꢀ
Page 6 of 11
ARTICLEꢀ
JournalꢀNameꢀ
[
2C8bti][L-tar]ꢀ<ꢀ[2C8bti][L-phe]2ꢀ≈ꢀ[2C8bti][Br]2ꢀ<ꢀ[2C8bti][sub]ꢀ asꢀaꢀconsequenceꢀofꢀabilityꢀofꢀhydroxylꢀgroupsꢀtVoieꢀwcoAroticrldeiOnnalitnee ꢀ
ꢀ[2C8bti][ad].ꢀ
DOI: 10.1039/C6RA12037G
theꢀ nitrogenꢀ ofꢀ theꢀ neutralꢀ imidazoleꢀ unitꢀ throughꢀ hydrogenꢀ
<
18ꢀ
AccordingꢀtoꢀdataꢀcollectedꢀforꢀtheꢀMHRꢀreaction, alsoꢀinꢀthisꢀ bondꢀformation.ꢀThisꢀcouldꢀinduceꢀaꢀdecreaseꢀinꢀitsꢀpropensityꢀ
caseꢀ theꢀ anionꢀ flexibilityꢀ playsꢀ aꢀ roleꢀ inꢀ determiningꢀ theꢀ toꢀactꢀasꢀaꢀbaseꢀtowardsꢀmalononitrile.ꢀꢀ
outcomeꢀ ofꢀ theꢀ reactionꢀ asꢀ accountedꢀ forꢀ byꢀ highꢀ yieldsꢀ Aꢀ differentꢀ analysisꢀ hasꢀ toꢀ supportꢀ dataꢀ obtainedꢀ inꢀ [L-pro]-ꢀ
obtainedꢀinꢀ[ad]-ꢀandꢀ[sub]-basedꢀTSDILsꢀ(Tableꢀ5,ꢀentriesꢀ2-3).ꢀ andꢀ [L-phe]-basedꢀ TSDILsꢀ (Tableꢀ 5,ꢀ entriesꢀ 6-7).ꢀ Indeed,ꢀ
Differently,ꢀ
asꢀ
previouslyꢀ
observedꢀ
forꢀ
someꢀ conversionꢀ valuesꢀ ofꢀ t-chalconeꢀ (76%ꢀ andꢀ 91%ꢀ respectively)ꢀ
18
naphthalenedisulfonate-basedꢀ TSDILs, ꢀ theꢀ extendedꢀ π- indicateꢀ anꢀ enhancedꢀ catalyticꢀ abilityꢀ ofꢀ theꢀ solventꢀ systemsꢀ
surfaceꢀofꢀ[R-BNphosph]ꢀanionꢀinducesꢀaꢀdropꢀinꢀyieldꢀvalue.ꢀ withꢀrespectꢀtoꢀ[tar]-basedꢀTSDILs,ꢀaccordingꢀtoꢀtheꢀincreaseꢀinꢀ
Probably,ꢀthisꢀanionꢀcanꢀeasilyꢀinteractꢀwithꢀtheꢀcationꢀthroughꢀ solventꢀ basicity.ꢀ Thisꢀ howeverꢀ bringsꢀ toꢀ aꢀ decreaseꢀ inꢀ theꢀ
π−πꢀstacking,ꢀloweringꢀtheꢀcationꢀconformationalꢀfreedomꢀandꢀ selectivityꢀofꢀtheꢀreactionꢀwithꢀtheꢀformationꢀofꢀproductsꢀ(3)ꢀ
makingꢀitꢀlessꢀavailableꢀtoꢀinteractꢀwithꢀtheꢀsubstrateꢀ(Tableꢀ5,ꢀ andꢀ(4)ꢀinꢀcomparableꢀamount.ꢀ
entryꢀ8).ꢀ Then,ꢀtheꢀwholeꢀofꢀdataꢀcollectedꢀseemsꢀtoꢀindicateꢀthatꢀtheꢀ
Onꢀ theꢀ otherꢀ hand,ꢀ theꢀ lowerꢀ catalyticꢀ abilityꢀ ofꢀ [tar]-basedꢀ outcomeꢀ ofꢀ theꢀ reactionꢀ isꢀ probablyꢀ determinedꢀ byꢀ aꢀ
TSDILsꢀ(Tableꢀ5,ꢀentriesꢀ4-5),ꢀwithꢀrespectꢀtoꢀ[ad]-ꢀandꢀ[sub]- concomitantꢀactionꢀofꢀbasicityꢀandꢀstructureꢀofꢀTSDILs.ꢀ
basedꢀTSDILs,ꢀcouldꢀbeꢀascribedꢀtoꢀaꢀlossꢀofꢀcatalyticꢀefficiencyꢀ
ꢀ
Tableꢀ5.ꢀPercentageꢀyieldsꢀofꢀproductsꢀ(3)ꢀandꢀ(4)ꢀandꢀconversionsꢀforꢀtheꢀMichaelꢀadditionꢀperformedꢀinꢀtheꢀpresenceꢀofꢀTSDILsꢀatꢀ30ꢀminꢀandꢀ25ꢀ
aꢀ
°
C.
bꢀ
bꢀ
bꢀ
Entryꢀ
TSDILꢀ
yieldꢀ%(3)
ꢀ
yieldꢀ%(4)
ꢀ
conversionꢀ%
ꢀ
1
ꢀ
[2C
[2C
[2C
[2C
8
bti][Br]
2
ꢀ
58ꢀ
0ꢀ
63ꢀ
2
3
ꢀ
ꢀ
8
bti][ad]ꢀ
>95ꢀ
74ꢀ
0ꢀ
0ꢀ
>95ꢀ
78ꢀ
8
bti][sub]ꢀ
4
ꢀ
8
bti][D-tar]ꢀ
51ꢀ
0ꢀ
57ꢀ
5
6
7
8
ꢀ
ꢀ
ꢀ
ꢀ
[2C
[2C
[2C
2
bti][R-BNphosph] ꢀ
8
bti][L-tar]ꢀ
bti][L-pro]
bti][L-phe]
52ꢀ
32ꢀ
56ꢀ
40ꢀ
0ꢀ
39ꢀ
35ꢀ
0ꢀ
56ꢀ
76ꢀ
91ꢀ
46ꢀ
8
2
ꢀ
8
2
ꢀ
[2C
8
a
ꢀ
b
Reactions wereꢀperformedꢀusingꢀaꢀ1/1/1ꢀsubstrate/TSDIL/MeOHꢀmolarꢀratio.ꢀ Yieldsꢀandꢀconversionsꢀwereꢀreproducibleꢀwithinꢀ4%.ꢀProductsꢀwereꢀ
isolatedꢀbyꢀflashꢀchromatography.ꢀ
Withꢀtheꢀonlyꢀexceptionꢀaboveꢀdiscussed,ꢀweꢀdidꢀnotꢀobservedꢀtheꢀ
Asꢀ aboveꢀ stated,ꢀ theꢀ useꢀ ofꢀ chiralꢀ dianionsꢀ inꢀ theꢀ preparationꢀ ofꢀ so-calledꢀ “chiralꢀ inductionꢀ solvent”.ꢀ Thisꢀ resultꢀ isꢀ notꢀ anomalous.ꢀ
TSDILsꢀ wasꢀ aimedꢀ toꢀ controlꢀ theꢀ reactionꢀ fromꢀ aꢀ stereochemicalꢀ Indeed,ꢀinꢀgeneral,ꢀgoodꢀorꢀhighꢀenantiomericꢀexcessesꢀhaveꢀbeenꢀ
pointꢀ ofꢀ view.ꢀ Thisꢀ isꢀ theꢀ reasonꢀ why,ꢀ afterꢀ purificationꢀ byꢀ flashꢀ reportedꢀ onlyꢀ inꢀ COSsꢀ andꢀ inꢀ theꢀ presenceꢀ ofꢀ catalystsꢀ havingꢀ
chromatography,ꢀproductsꢀobtainedꢀinꢀchiralꢀTSDILsꢀwereꢀanalysedꢀ provedꢀchiralꢀinductionꢀabilityꢀlikeꢀCinchonaꢀalkaloids.ꢀTomaꢀetꢀal.ꢀ
byꢀHPLCꢀusingꢀaꢀchiralꢀpackꢀcolumnꢀtoꢀassessꢀprobableꢀenantiomericꢀ observedꢀ aꢀ veryꢀ differentꢀ behaviourꢀ testingꢀ organocatalystsꢀ inꢀ
27
excess.ꢀUnfortunately,ꢀourꢀresultsꢀwereꢀnotꢀpromisingꢀtoꢀthisꢀaim.ꢀ monocationicꢀILs. ꢀAccordingꢀtoꢀtheꢀaboveꢀreport,ꢀtheꢀlowꢀ“chiralꢀ
Indeed,ꢀ weꢀ obtainedꢀ aꢀ lowꢀ enantiomericꢀ excessꢀ onlyꢀ inꢀ theꢀ inductionꢀability”ꢀofꢀourꢀTSDILsꢀcouldꢀbeꢀascribedꢀtoꢀtheꢀfactꢀthatꢀ
presenceꢀofꢀ[2C
8
bti][R-BNphosph]
2
ꢀ(eeꢀ=ꢀ10ꢀ%).ꢀꢀ
theꢀ directꢀ additionꢀ ofꢀ nucleophileꢀ toꢀ theꢀ ketoneꢀ isꢀ fasterꢀ withꢀ
Inꢀ theꢀ attemptꢀ toꢀ improveꢀ theꢀ aboveꢀ result,ꢀ weꢀ performedꢀ theꢀ respectꢀ toꢀ theꢀ chiralꢀ adductꢀ formationꢀ thatꢀ shouldꢀ improveꢀ theꢀ
reactionꢀatꢀ4ꢀ°Cꢀandꢀusingꢀtolueneꢀasꢀcosolvent.ꢀIndeed,ꢀitꢀisꢀwellꢀ stereochemicalꢀcontrolꢀofꢀtheꢀtargetꢀreaction.ꢀ
knownꢀ thatꢀ theꢀ decreaseꢀ inꢀ temperatureꢀ andꢀ theꢀ lowꢀ polarityꢀ ofꢀ
solventꢀ disfavourꢀ racemizationꢀ processes.ꢀ Onꢀ thisꢀ subject,ꢀ someꢀ
Conclusionsꢀ
yearsꢀagoꢀDengꢀetꢀal.,ꢀperformingꢀMichaelꢀadditionꢀofꢀmalononitrileꢀ
toꢀα,β-unsaturatedꢀketones,ꢀinꢀtheꢀpresenceꢀofꢀCinchonaꢀalkaloidsꢀ
Theꢀ searchꢀ forꢀ syntheticꢀ processesꢀ ofꢀ lowꢀ environmentalꢀ impactꢀ
asꢀcatalysts,ꢀobtainedꢀhighꢀenantiomericꢀexcessesꢀonlyꢀinꢀlowꢀpolarꢀ
22
inducedꢀusꢀtoꢀtestꢀsomeꢀfunctionalisedꢀDILsꢀinꢀtheꢀMichaelꢀaddition.ꢀ
Resultsꢀcollectedꢀshedꢀlightꢀonꢀtheꢀadvantageꢀofꢀboundingꢀaꢀbasicꢀ
catalystꢀ onꢀ anꢀ ionicꢀ tagꢀ asꢀ testifiedꢀ byꢀ theꢀ significantꢀ decreaseꢀ inꢀ
reactionꢀtimeꢀdetectedꢀonꢀgoingꢀfromꢀtheꢀuseꢀofꢀtheꢀcatalystꢀinꢀDILꢀ
solutionꢀtoꢀtheꢀuseꢀofꢀfunctionalisedꢀDILs.ꢀ
solvents. ꢀ
Inꢀ ourꢀ experimentalꢀ conditions,ꢀ weꢀ obtainedꢀ aꢀ 55%ꢀ yieldꢀ inꢀ
dicyanideꢀ (3)ꢀ atꢀ 5.50ꢀ h,ꢀ butꢀ withꢀ aꢀ significantꢀ increaseꢀ inꢀ
enantiomericꢀexcessꢀ(eeꢀ=ꢀ35%).ꢀTheꢀvalueꢀobtainedꢀisꢀhigherꢀthanꢀ
theꢀ oneꢀ reportedꢀ byꢀ Baoꢀ etꢀ al.,ꢀ studyingꢀ theꢀ enantioselectiveꢀ
additionꢀ ofꢀ diethylmalonateꢀ toꢀ 1,3-diphenyl-prop-2-ene-1-oneꢀ inꢀ
AllꢀfunctionalisedꢀDILsꢀareꢀableꢀtoꢀgiveꢀhighꢀconversionsꢀandꢀyieldsꢀ
underꢀ mildꢀ conditions.ꢀ Theyꢀ allowꢀ employingꢀ aꢀ
45
imidazoliumꢀbasedꢀchiralꢀILsꢀ(eeꢀ=ꢀ24ꢀ%). ꢀꢀ
6
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 7 of 11
Please Rꢀ d So Cꢀ n oA t dꢀ av da j nu cs teꢀ ms arginsꢀ
JournalꢀNameꢀ
ꢀARTICLEꢀ
−4ꢀ
44
View Article Online
-
catalyst/substrate/solventꢀ stoichiometricꢀ ratioꢀ andꢀ promoteꢀ theꢀ 5Ÿ10 M).ꢀBasicꢀstrengthꢀwasꢀexpressedꢀbyꢀaꢀbasicityꢀfunctionꢀ(H ) ꢀ
DOI: 10.1039/C6RA12037G
reactionꢀinꢀsignificantlyꢀshorterꢀreactionꢀtimesꢀwithꢀrespectꢀtoꢀtheꢀ definedꢀbyꢀtheꢀfollowingꢀeqꢀ1.ꢀ
onesꢀ soꢀ farꢀ reportedꢀ forꢀ theꢀ sameꢀ reactionꢀ inꢀ COSsꢀ and,ꢀ inꢀ someꢀ
−
cases,ꢀ alsoꢀ inꢀ ILꢀ solution.ꢀ Thisꢀ certainlyꢀ representsꢀ anꢀ advantageꢀ
fromꢀanꢀenvironmentalꢀpointꢀofꢀviewꢀalsoꢀconsideringꢀtheꢀfactꢀthatꢀ
H
-
ꢀ=ꢀpKHIꢀ+ꢀlog[I ]/[HI]ꢀꢀ ꢀ
ꢀ
ꢀ
(1)ꢀ
theseꢀTSDILsꢀallowꢀeasilyꢀobtainingꢀofꢀusefulꢀorganicꢀintermediatesꢀ whereꢀ pKHIꢀ isꢀ theꢀ logarithmꢀ ofꢀ theꢀ dissociationꢀ constantꢀ ofꢀ theꢀ
−
likeꢀnitrileꢀfunctionalisedꢀproducts.ꢀ
indicatorꢀ used,ꢀ andꢀ [HI]ꢀ andꢀ [I ]ꢀ areꢀ theꢀ concentrationꢀ ofꢀ theꢀ
−
DataꢀcollectedꢀpointꢀoutꢀthatꢀtheꢀcatalyticꢀefficiencyꢀofꢀtheꢀTSDILsꢀisꢀ indicatorꢀ andꢀ itsꢀ conjugatedꢀ base,ꢀ respectively.ꢀ Theꢀ [I ]/[HI]ꢀ ratioꢀ
theꢀresultꢀofꢀaꢀcombinedꢀactionꢀofꢀtheirꢀbasicityꢀandꢀanionꢀstructure.ꢀ wasꢀ determinedꢀ spectrophotometricallyꢀ afterꢀ theꢀ evaluationꢀ ofꢀ
Asꢀ forꢀ basicity,ꢀ althoughꢀ itꢀ favoursꢀ t-chalconeꢀ conversion,ꢀ itꢀ alsoꢀ indicatorꢀεꢀvalue.ꢀ
inducesꢀaꢀdropꢀinꢀtheꢀselectivityꢀofꢀtheꢀreaction.ꢀOnꢀtheꢀotherꢀhand,ꢀ
ReactionꢀConditions.ꢀTheꢀcatalyticꢀreactionsꢀwereꢀperformedꢀusingꢀ
aꢀTSDIL/t-chalconeꢀmoleꢀratioꢀofꢀ1ꢀandꢀaꢀmalononitrile/t-chalconeꢀ
moleꢀratioꢀofꢀ1.13.ꢀInꢀaꢀtypicalꢀexperimentꢀTSDILꢀ(≈ꢀ100ꢀmg,ꢀ0.154ꢀ
mmol),ꢀt-chalconeꢀ(30ꢀmg,ꢀ0.154ꢀmmol)ꢀandꢀmalononitrileꢀ(≈ꢀ12ꢀmg,ꢀ
takingꢀintoꢀaccountꢀanionꢀstructure,ꢀinformationꢀobtainedꢀindicatesꢀ
thatꢀbestꢀperformancesꢀareꢀdetectedꢀinꢀtheꢀpresenceꢀofꢀanionsꢀableꢀ
toꢀwarrantꢀtheꢀconformationalꢀfreedomꢀofꢀtheꢀcationꢀandꢀitsꢀabilityꢀ
toꢀactꢀbothꢀasꢀsolventꢀandꢀcatalyst.ꢀ
0
.178ꢀmmol)ꢀwereꢀweighedꢀintoꢀaꢀ4ꢀmLꢀscrewꢀcappedꢀvial,ꢀthenꢀanꢀ
However,ꢀ theꢀ highꢀ catalyticꢀ abilityꢀ bringsꢀ aꢀ lossꢀ inꢀ theꢀ
stereochemicalꢀ control,ꢀ asꢀ testifiedꢀ byꢀ theꢀ factꢀ thatꢀ moderateꢀ
enantiomericꢀexcessꢀwasꢀobtainedꢀonlyꢀinꢀtheꢀpresenceꢀofꢀtheꢀmostꢀ
rigidꢀbinaphthylꢀphosphateꢀanion,ꢀatꢀlowꢀtemperature.ꢀ
appropriateꢀ amountꢀ ofꢀ cosolventꢀ wasꢀ added.ꢀ Theꢀ reactionꢀ wasꢀ
performedꢀunderꢀmagneticꢀstirringꢀatꢀroomꢀtemperatureꢀorꢀatꢀ4ꢀ°Cꢀ
andꢀ wasꢀ followedꢀ viaꢀ TLCꢀ (eluent:ꢀ petroleumꢀ ether/ethylꢀ acetateꢀ
5
/1).ꢀ Unfortunately,ꢀ theꢀ lowꢀ solubilityꢀ ofꢀ theꢀ reactionꢀ productsꢀ inꢀ
diethylꢀetherꢀdidꢀnotꢀallowꢀtheirꢀextractionꢀfromꢀTSDILs.ꢀSo,ꢀMeOHꢀ
wasꢀ addedꢀ toꢀ theꢀ reactionꢀ mixtureꢀ inꢀ orderꢀ toꢀ separateꢀ theꢀ
productsꢀ withꢀ silicaꢀ flashꢀ chromatographyꢀ (eluent,ꢀ petroleumꢀ
ether/ethylꢀ acetateꢀ 10/1ꢀ andꢀ 5/1).ꢀ Theꢀ organicꢀ phaseꢀ wasꢀ
concentratedꢀinꢀvacuumꢀandꢀsolubilizedꢀinꢀ2-propanolꢀtoꢀdetermineꢀ
enantiomericꢀexcessꢀbyꢀHPLC.ꢀꢀ
ExperimentalꢀSectionꢀ
Materialsꢀ andꢀ Measurements.ꢀ Allꢀ TSDILsꢀ andꢀ [m-C
8
im][Br]
ꢀ α, α’-1,3-dibromoxylene,ꢀ
1-bromooctane,ꢀ imidazole,ꢀ
2
ꢀ wereꢀ
15,ꢀ 17
preparedꢀ asꢀ previouslyꢀ reported.
,3,5-tris(bromomethyl)benzene,ꢀ
1
sodiumꢀhydroxide,ꢀAmberliteꢀIRAꢀ400ꢀresin,ꢀ1,4-butanedicarboxylicꢀ
acid,ꢀ1,6-hexanedicarboxylicꢀacid,ꢀD-tartaricꢀacid,ꢀL-tartaricꢀacid,ꢀL-
HPLCꢀanalysis.ꢀHPLCꢀwasꢀperformedꢀusingꢀaꢀChiralpakꢀAS-Hꢀcolumnꢀ
withꢀeluentꢀ2-propanol/hexaneꢀ=ꢀ30/70,ꢀflowꢀrateꢀ0.5ꢀmL/minꢀandꢀλꢀ
proline,ꢀ
L-phenylalanine,ꢀ
(R)-(−)-1,1’-binaphthyl-2,2’-diylꢀ
=
ꢀ234ꢀnm:ꢀtmonocyanideꢀ=ꢀ15.2ꢀmin,ꢀtminorꢀdicyanideꢀ=ꢀ19ꢀmin,ꢀtmajorꢀdicyanideꢀ=ꢀ
hydrogenphosphate,ꢀ t-chalcone,ꢀ malononitrile,ꢀ potassiumꢀ
carbonate,ꢀ 1-methylimidazole,ꢀ p-nitrophenol,ꢀ bromocresolꢀ green,ꢀ
2
2ꢀmin.ꢀ
1
-propanol,ꢀ dimethylformamide,ꢀ tetrahydrofuran,ꢀ acetonitrile,ꢀ
1
-[1ʹ-Methyleneimidazole]-3,5-di-[1ʹ-methylen-3ʹ-
dietylꢀ ether,ꢀ tolueneꢀ andꢀ 1,4-dioxaneꢀ wereꢀ analyticalꢀ reagentsꢀ
purchasedꢀ fromꢀ commercialꢀ sourcesꢀ andꢀ usedꢀ asꢀ received.ꢀ
Chloroformꢀandꢀmethanolꢀwereꢀdistilledꢀbeforeꢀuse.ꢀꢀ
octylimidazolium]-benzeneꢀD-tartrateꢀ([2C
Aꢀlightꢀyellowꢀwaxyꢀsolid.ꢀm.p.:ꢀ35-38ꢀ°C.ꢀ[α]ꢀ=ꢀ-5.57ꢀ°ꢀ(C=1Ÿ10 ꢀMꢀinꢀ
CH OH).ꢀ H-NMRꢀ(300ꢀMHz;ꢀdmso-d );ꢀδ/ppm:ꢀ0.83ꢀ(t,ꢀJH–H=ꢀ8ꢀHz,ꢀ6ꢀ
3 6
8
bti][D-tar]).ꢀYieldꢀ94ꢀ%.ꢀ
-2
1
H);ꢀ1.24ꢀ(m,ꢀ20ꢀH);ꢀ1.78ꢀ(m,ꢀ4ꢀH);ꢀ3.79ꢀ(s,ꢀ2ꢀH);ꢀ4.17ꢀ(m,ꢀ4ꢀH);ꢀ5.17ꢀ
(m,ꢀ2ꢀH);ꢀ5.43ꢀ(m,ꢀ4ꢀH);ꢀ7.13ꢀ(m,ꢀ3ꢀH);ꢀ7.71ꢀ(m,ꢀ7ꢀH);ꢀ9.61ꢀ(m,ꢀ2ꢀH).ꢀ
1
13
H-NMRꢀ andꢀ C-NMRꢀ spectraꢀ wereꢀ recordedꢀ usingꢀ 300ꢀ MHzꢀ 13
C-NMRꢀ(300ꢀMHz;ꢀdmso-d
9.5;ꢀ 31.4;ꢀ 49.2;ꢀ 51.3;ꢀ 71.9;ꢀ 119.4;ꢀ 122.5;ꢀ 126.8;ꢀ 127.9;ꢀ 128.9;ꢀ
129.4;ꢀ136.3;ꢀ136.6;ꢀ137.5;ꢀ139.4;ꢀ174.8.ꢀElementalꢀAnal.ꢀCalcd.ꢀ(%)ꢀ
forꢀC38 6ꢀ(692.89):ꢀC,ꢀ65.87;ꢀH,ꢀ8.15;ꢀN,ꢀ12.13.ꢀFound:ꢀC,ꢀ65.69;ꢀ
H,ꢀ8.12;ꢀN,ꢀ12.15.ꢀ
6
);ꢀδ/ppm:ꢀ14.1;ꢀ22.3;ꢀ25.7;ꢀ28.5;ꢀ28.7;ꢀ
nuclearꢀ magneticꢀ resonanceꢀ spectrometer.ꢀ Chemicalꢀ shiftsꢀ wereꢀ
reportedꢀrelativeꢀtoꢀSiMe .ꢀ
2
4
56 6
H N O
Polarimetricꢀ Measurements.ꢀ Solutionsꢀ ofꢀ chiralꢀ TSDILsꢀ wereꢀ
-2
preparedꢀinꢀvolumetricꢀflasksꢀ(Cꢀ=ꢀ1Ÿ10 ꢀM).ꢀOpticalꢀrotationsꢀwereꢀ
1
-[1ʹ-Methyleneimidazole]-3,5-di-[1ʹ-methylen-3ʹ-
measuredꢀ usingꢀ aꢀ glassꢀ polarimetricꢀ cellꢀ (lightꢀ pathꢀ 1ꢀ dm)ꢀ andꢀ
octylimidazolium]-benzeneꢀ L-tartrateꢀ ([2C bti][L-tar]).ꢀ Yieldꢀ 95ꢀ %.ꢀ
8
-2
obtainedꢀ asꢀ theꢀ averageꢀ valueꢀ overꢀ 50ꢀ readings.ꢀ Measurementsꢀ Aꢀlightꢀyellowꢀwaxyꢀsolid.ꢀm.p.:ꢀ35-38ꢀ°C.ꢀ[α]ꢀ=ꢀ5.59ꢀ°ꢀ(C=1Ÿ10 ꢀMꢀinꢀ
1
CH
H);ꢀ1.30ꢀ(m,ꢀ20ꢀH);ꢀ1.84ꢀ(m,ꢀ4ꢀH);ꢀ3.88ꢀ(s,ꢀ2ꢀH);ꢀ4.24ꢀ(m,ꢀ4ꢀH);ꢀ5.25ꢀ
m,ꢀ2ꢀH);ꢀ5.50ꢀ(m,ꢀ4ꢀH);ꢀ7.22ꢀ(m,ꢀ3ꢀH);ꢀ7.87ꢀ(m,ꢀ7ꢀH);ꢀ9.70ꢀ(m,ꢀ2ꢀH).ꢀ
3 6
OH).ꢀ H-NMRꢀ(300ꢀMHz;ꢀdmso-d );ꢀδ/ppm:ꢀ0.90ꢀ(t,ꢀJH–H=ꢀ8ꢀHz,ꢀ6ꢀ
wereꢀperformedꢀatꢀ25ꢀ°Cꢀandꢀ589ꢀnm.ꢀ
(
1
3
BaseꢀStrength.ꢀAꢀsuitableꢀamountꢀofꢀTSDILꢀwasꢀaddedꢀtoꢀaꢀmethanolꢀ
6
C-NMRꢀ(300ꢀMHz;ꢀdmso-d );ꢀδ/ppm:ꢀ14.0;ꢀ22.2;ꢀ25.7;ꢀ28.5;ꢀ28.6;ꢀ
solutionꢀ ofꢀ theꢀ indicator,ꢀ observingꢀ aꢀ colorꢀ change.ꢀ Theꢀ resultingꢀ 29.6;ꢀ 31.3;ꢀ 49.1;ꢀ 56.1;ꢀ 72.0;ꢀ 119.4;ꢀ 122.8;ꢀ 123.2;ꢀ 127.9;ꢀ 128.8;ꢀ
1
36.4;ꢀ136.5;ꢀ137.5;ꢀ139.2;ꢀ139.5;ꢀ175.1.ꢀElementalꢀAnal.ꢀCalcd.ꢀ(%)ꢀ
forꢀC38 6ꢀ(692.89):ꢀC,ꢀ65.87;ꢀH,ꢀ8.15;ꢀN,ꢀ12.13.ꢀFound:ꢀC,ꢀ65.73;ꢀ
H,ꢀ8.17;ꢀN,ꢀ12.11.ꢀ
solutionꢀ wasꢀ analyzedꢀ byꢀ meansꢀ ofꢀ UV−visꢀ spectroscopy,ꢀ usingꢀ aꢀ
quarzꢀ cuvetteꢀ withꢀ lightꢀ pathꢀ ofꢀ 0.2ꢀ cm.ꢀ Theꢀ indicatorsꢀ used,ꢀ theꢀ
relativeꢀ concentrations,ꢀ andꢀ theꢀ TSDILꢀ concentrationꢀ wereꢀ asꢀ
56 6
H N O
−
4
follows:ꢀ p-nitrophenolꢀ (pKHIꢀ =ꢀ 11.30;ꢀ [HI]ꢀ =ꢀ 2Ÿ10 ꢀ M;ꢀ [TSDIL]ꢀ =ꢀ 1-[1ʹ-Methyleneimidazole]-3,5-di-[1ʹ-methylen-3ʹ-
−
3
−4
octylimidazolium]-benzeneꢀ L-prolinateꢀ ([2C
9
8
bti][L-pro]
2
).ꢀ Yieldꢀ
2
Ÿ10 ꢀM);ꢀbromocresolꢀgreenꢀ(pKHIꢀ=ꢀ9.8;ꢀ[HI]ꢀ=ꢀ1Ÿ10 ꢀM;ꢀ[TSDIL]ꢀ=ꢀ
-
2
1
3
4ꢀ%.ꢀAꢀyellowꢀwaxyꢀsolid.ꢀ[α]ꢀ=ꢀ-19.8ꢀ°ꢀ(C=1Ÿ10 ꢀMꢀinꢀCH OH).ꢀ H-
NMRꢀ(400ꢀMHz;ꢀdmso-d
6
);ꢀδ/ppm:ꢀ0.84ꢀ(t,ꢀJH–H=ꢀ8ꢀHz,ꢀ6ꢀH);ꢀ1.23ꢀ(m,ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ7ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Please Rꢀ d So Cꢀ n oA t dꢀ av da j nu cs teꢀ ms arginsꢀ
Page 8 of 11
ARTICLEꢀ
JournalꢀNameꢀ
2
0ꢀH);ꢀ1.50ꢀ(m,ꢀ6ꢀH);ꢀ1.77ꢀ(m,ꢀ6ꢀH);ꢀ2.95ꢀ(m,ꢀ4ꢀH);ꢀ4.16ꢀ(m,ꢀ4ꢀH);ꢀ5.16ꢀ 9.ꢀ
F.ꢀD’Anna,ꢀS.ꢀMarulloꢀandꢀR.ꢀNoto,ꢀJ.ꢀOrg.ꢀChVeiemw.,Aꢀr2ti0cl0e8O,nꢀ7lin3e,ꢀ
6224-6228.ꢀ
F.ꢀD’Anna,ꢀS.ꢀMarulloꢀandꢀR.ꢀNoto,ꢀJ.ꢀOrg.ꢀChem.,ꢀ2010,ꢀ75,ꢀ
67-771.ꢀ
F.ꢀ D'Annaꢀ andꢀ R.ꢀ Noto,ꢀ Eur.ꢀ J.ꢀ Org.ꢀ Chem.,ꢀ 2014,ꢀ 2014,ꢀ
201-4223.ꢀ
D.ꢀFang,ꢀJ.ꢀYangꢀandꢀC.ꢀJiao,ꢀACSꢀCatal.,ꢀ2011,ꢀ1,ꢀ42-47.ꢀ
H.-F.ꢀ Liu,ꢀ F.-X.ꢀ Zeng,ꢀ L.ꢀ Deng,ꢀ B.ꢀ Liao,ꢀ H.ꢀ Pangꢀ andꢀ Q.-X.ꢀ
Guo,ꢀGreenꢀChem.,ꢀ2013,ꢀ15,ꢀ81-84.ꢀ
H.ꢀ A.ꢀ Beejapur,ꢀ V.ꢀ Campisciano,ꢀ F.ꢀ Giacaloneꢀ andꢀ M.ꢀ
Gruttadauria,ꢀAdv.ꢀSynth.ꢀCatal.,ꢀ2015,ꢀ357,ꢀ51-58.ꢀ
F.ꢀ D'Anna,ꢀ F.ꢀ Ferranteꢀ andꢀ R.ꢀ Noto,ꢀChem.ꢀ Eur.ꢀ J.,ꢀ 2009,ꢀ
15,ꢀ13059-13068.ꢀ
(
(
m,ꢀ2ꢀH);ꢀ5.44ꢀ(m,ꢀ4ꢀH);ꢀ6.87ꢀ(s,ꢀ1ꢀH);ꢀ7.14ꢀ(m,ꢀ2ꢀH);ꢀ7.33ꢀ(s,ꢀ1ꢀH);ꢀ7.69ꢀ
m,ꢀ2ꢀH);ꢀ7.86ꢀ(m,ꢀ4ꢀH);ꢀ9.92ꢀ(m,ꢀ2ꢀH).ꢀ C-NMRꢀ(300ꢀMHz;ꢀdmso-d );ꢀ
6
DOI: 10.1039/C6RA12037G
13
1
1
0.ꢀ
1.ꢀ
δ/ppm:ꢀ 14.4;ꢀ 22.5;ꢀ 25.9;ꢀ 26.1,ꢀ 28.8;ꢀ 28.9;ꢀ 29.7;ꢀ 31.8;ꢀ 47.7;ꢀ 49.4;ꢀ
7
4
1
C
8
9.5;ꢀ51.7;ꢀ119.9;ꢀ122.9;ꢀ123.1;ꢀ127.1;ꢀ128.3;ꢀ129.2;ꢀ129.8;ꢀ136.8;ꢀ
36.9;ꢀ 137.4;ꢀ 137.9;ꢀ 139.5;ꢀ 139.7.ꢀ Elementalꢀ Anal.ꢀ Calcd.ꢀ (%)ꢀ forꢀ
4
44 68 8
H N O4ꢀ(772.03):ꢀC,ꢀ68.36;ꢀH,ꢀ8.87;ꢀN,ꢀ14.49.ꢀFound:ꢀC,ꢀ68.20;ꢀH,ꢀ
.89;ꢀN,ꢀ14.52.ꢀ
1
1
2.ꢀ
3.ꢀ
1
-[1ʹ-Methyleneimidazole]-3,5-di-[1ʹ-methylen-3ʹ-
1
4.ꢀ
octylimidazolium]-benzeneꢀ L-phenylalaninateꢀ ([2C
8
bti][L-phe1]
Yieldꢀ95ꢀ%.ꢀAnꢀorangeꢀoil.ꢀ[α]ꢀ=ꢀ-6.48ꢀ°ꢀ(C=1Ÿ10 ꢀMꢀinꢀCH OH).ꢀ H-
NMRꢀ(400ꢀMHz;ꢀdmso-d
);ꢀδ/ppm:ꢀ0.82ꢀ(t,ꢀJH–H=ꢀ6ꢀHz,ꢀ6ꢀH);ꢀ1.18ꢀ(m,ꢀ 15.ꢀ
0ꢀH);ꢀ1.77ꢀ(m,ꢀ4ꢀH);ꢀ3.03ꢀ(dd,ꢀJ1H–H=ꢀ9ꢀHz,ꢀJ2H–H=ꢀ6ꢀHz,ꢀ4ꢀH);ꢀ4.14ꢀ(m,ꢀ
ꢀH);ꢀ5.17ꢀ(m,ꢀ2ꢀH);ꢀ5.42ꢀ(m,ꢀ4ꢀH);ꢀ6.88ꢀ(s,ꢀ1ꢀH);ꢀ7.12ꢀ(m,ꢀ3ꢀH);ꢀ7.19ꢀ 16.ꢀ
2
).ꢀ
-2
3
6
2
4
F.ꢀD’Anna,ꢀP.ꢀVitaleꢀandꢀR.ꢀNoto,ꢀJ.ꢀOrg.ꢀChem.,ꢀ2009,ꢀ74,ꢀ
(
m,ꢀ8ꢀH);ꢀ7.35ꢀ(s,ꢀ1ꢀH);ꢀ7.71ꢀ(m,ꢀ5ꢀH);ꢀ7.90ꢀ(m,ꢀ2ꢀH);ꢀ9.89ꢀ(m,ꢀ2ꢀH).ꢀ
6
224-6230.ꢀ
1
3
6
C-NMRꢀ(300ꢀMHz;ꢀdmso-d );ꢀδ/ppm:ꢀ14.2;ꢀ22.5;ꢀ26.0;ꢀ28.8;ꢀ29.0;ꢀ
9.8;ꢀ 30.2;ꢀ 31.6;ꢀ 49.4;ꢀ 49.5;ꢀ 119.8;ꢀ 122.9;ꢀ 127.9;ꢀ 128.3;ꢀ 129.2;ꢀ
30.0;ꢀ136.8;ꢀ137.9;ꢀ139.3;ꢀ139.5;ꢀ139.6.ꢀElementalꢀAnal.ꢀCalcd.ꢀ(%)ꢀ
1
7.ꢀ
F.ꢀD'Anna,ꢀH.ꢀQ.ꢀNimalꢀGunaratne,ꢀG.ꢀLazzara,ꢀR.ꢀNoto,ꢀC.ꢀ
Rizzoꢀ andꢀ K.ꢀ R.ꢀ Seddon,ꢀ Org.ꢀ Biomol.ꢀ Chem.,ꢀ 2013,ꢀ 11,ꢀ
2
1
5
836-5846.ꢀ
C.ꢀRizzo,ꢀF.ꢀD’Anna,ꢀS.ꢀMarulloꢀandꢀR.ꢀNoto,ꢀJ.ꢀOrg.ꢀChem.,ꢀ
014,ꢀ79,ꢀ8678-8683.ꢀ
J.ꢀ M.ꢀ Humphreyꢀ andꢀ A.ꢀ R.ꢀ Chamberlin,ꢀ Chem.ꢀ Rev.ꢀ
Washington,ꢀDC,ꢀU.ꢀS.),ꢀ1997,ꢀ97,ꢀ2243-2266.ꢀ
forꢀC52
H,ꢀ8.29;ꢀN,ꢀ12.79.ꢀ
72 8 4
H N O (ꢀ873.18):ꢀC,ꢀ71.53;ꢀH,ꢀ8.31;ꢀN,ꢀ12.83.ꢀFound:ꢀC,ꢀ71.59;ꢀ
1
1
2
8.ꢀ
9.ꢀ
0.ꢀ
2
1
-[1ʹ-Methyleneimidazole]-3,5-di-[1ʹ-methylen-3ʹ-
(
octylimidazolium]-benzeneꢀ
phosphateꢀ ([2C bti][R-BNphosph]
(R)-(−)-1,1ʹ-Binaphthyl-2,2ʹ-diylꢀ
2
).ꢀ Yieldꢀ 97ꢀ %.ꢀ Aꢀ lightꢀ yellowꢀ
S.ꢀ Lin,ꢀ Y.ꢀ Weiꢀ andꢀ F.ꢀ Liang,ꢀ Chem.ꢀ Commun.,ꢀ 2012,ꢀ 48,ꢀ
9879-9881.ꢀ
E.ꢀ Wei,ꢀ B.ꢀ Liu,ꢀ S.ꢀ Linꢀ andꢀ F.ꢀ Liang,ꢀ Org.ꢀ Biomol.ꢀ Chem.,ꢀ
2014,ꢀ12,ꢀ6389-6392.ꢀ
X.ꢀLi,ꢀL.ꢀCun,ꢀC.ꢀLian,ꢀL.ꢀZhong,ꢀY.ꢀChen,ꢀJ.ꢀLiao,ꢀJ.ꢀZhuꢀandꢀJ.ꢀ
Deng,ꢀOrg.ꢀBiomol.ꢀChem.,ꢀ2008,ꢀ6,ꢀ349-353.ꢀ
A.ꢀRusso,ꢀA.ꢀPerfettoꢀandꢀA.ꢀLattanzi,ꢀ Adv.ꢀSynth.ꢀCatal.,ꢀ
8
-
2
1
powder.ꢀm.p.:ꢀ134-136ꢀ°C.ꢀ[α]ꢀ=ꢀ-386.36ꢀ(C=1Ÿ10 ꢀMꢀinꢀCH
NMRꢀ (300ꢀ MHz;ꢀ dmso-d );ꢀ δ/ppm:ꢀ 0.82ꢀ (m,ꢀ 6ꢀ H);ꢀ 1.17ꢀ (m,ꢀ 20ꢀ H);ꢀ 21.ꢀ
.62ꢀ(m,ꢀ4ꢀH);ꢀ4.00ꢀ(m,ꢀ4ꢀH);ꢀ5.26ꢀ(m,ꢀ2ꢀH);ꢀ5.39ꢀ(m,ꢀ4ꢀH);ꢀ7.12ꢀ(s,ꢀ1ꢀ
3
OH).ꢀ H-
6
1
1
H);ꢀ7.35ꢀ(m,ꢀ20ꢀH);ꢀ7.60ꢀ(s,ꢀ1ꢀH);ꢀ7.76ꢀ(m,ꢀ4ꢀH);ꢀ8.00ꢀ(dd,ꢀJ H–H=ꢀ6ꢀHz,ꢀ
2
2
2
2
2
2
2.ꢀ
3.ꢀ
4.ꢀ
5.ꢀ
6.ꢀ
7.ꢀ
2
13
J
H–H=ꢀ 3ꢀ Hz,ꢀ 8ꢀ H);ꢀ 9.45ꢀ (m,ꢀ 2ꢀ H).ꢀ C-NMRꢀ (300ꢀ MHz;ꢀ dmso-d
6
);ꢀ
δ/ppm:ꢀ 14.1;ꢀ 22.5;ꢀ 25.9;ꢀ 28.8;ꢀ 28.9;ꢀ 29.7;ꢀ 31.6;ꢀ 49.4;ꢀ 51.9;ꢀ 122.2;ꢀ
1
1
forꢀ C74
7
22.3;ꢀ123.0;ꢀ123.1;ꢀ123.2;ꢀ124.9;ꢀ126.5;ꢀ126.7;ꢀ128.8;ꢀ130.1;ꢀ130.7;ꢀ
32.4;ꢀ136.6;ꢀ136.7;ꢀ136.9;ꢀ150.6;ꢀ150.7.ꢀElementalꢀAnal.ꢀCalcdꢀ(%)ꢀ
2
009,ꢀ351,ꢀ3067-3071.ꢀ
H.ꢀ Hagiwara,ꢀ T.ꢀ Okabe,ꢀ T.ꢀ Hoshiꢀ andꢀ T.ꢀ Suzuki,ꢀ J.ꢀ Mol.ꢀ
Catal.ꢀA:ꢀChem.,ꢀ2004,ꢀ214,ꢀ167-174.ꢀ
P.ꢀ Kotrusz,ꢀ S.ꢀ Toma,ꢀ H.-G.ꢀ Schmalzꢀ andꢀ A.ꢀ Adler,ꢀ Eur.ꢀ J.ꢀ
Org.ꢀChem.,ꢀ2004,ꢀ2004,ꢀ1577-1583.ꢀ
76 6 8
H N O P2ꢀ (1238.52):ꢀ C,ꢀ 71.71;ꢀ H,ꢀ 6.18;ꢀ N,ꢀ 6.78.ꢀ Found:ꢀ C,ꢀ
1.60;ꢀH,ꢀ6.16;ꢀN,ꢀ6.76.ꢀ
M.ꢀMečiarováꢀandꢀŠ.ꢀToma,ꢀChem.ꢀEur.ꢀJ.,ꢀ2007,ꢀ13,ꢀ1268-
Acknowledgementsꢀ
1
272.ꢀ
WeꢀthankꢀMIURꢀ(FIRBꢀ2010RBFR10BF5V)ꢀforꢀfinancialꢀsupport.ꢀ
M.ꢀ Meciarova,ꢀ S.ꢀ Tomaꢀ andꢀ P.ꢀ Kotrusz,ꢀ Org.ꢀ Biomol.ꢀ
Chem.,ꢀ2006,ꢀ4,ꢀ1420-1424.ꢀ
A.ꢀ Chinnappanꢀ andꢀ H.ꢀ Kim,ꢀ Chem.ꢀ Eng.ꢀ J.ꢀ (Lausanne),ꢀ
ꢀ
ꢀ
28.ꢀ
2
012,ꢀ187,ꢀ283-288.ꢀ
2
3
3
9.ꢀ
0.ꢀ
1.ꢀ
F.ꢀD'Anna,ꢀS.ꢀMarullo,ꢀP.ꢀVitaleꢀandꢀR.ꢀNoto,ꢀEur.ꢀJ.ꢀOrg.ꢀ
Chem.,ꢀ2011,ꢀ2011,ꢀ5681-5689.ꢀ
X.ꢀ Hanꢀ andꢀ D.ꢀ W.ꢀ Armstrong,ꢀ Org.ꢀ Lett.,ꢀ 2005,ꢀ 7,ꢀ 4205-
Referencesꢀ
ꢀ
ꢀ
ꢀ
4
208.ꢀ
A.ꢀBottoni,ꢀM.ꢀLombardo,ꢀG.ꢀP.ꢀMiscione,ꢀE.ꢀMontroni,ꢀA.ꢀ
Quintavallaꢀ andꢀ C.ꢀ Trombini,ꢀ ChemCatChem,ꢀ 2013,ꢀ 5,ꢀ
1
.ꢀ
.ꢀ
P.ꢀWasserscheidꢀandꢀT.ꢀWelton,ꢀIonicꢀLiquidsꢀinꢀSynthesis,ꢀ
Wiley-VCH,ꢀWeinheim,ꢀGermany,ꢀ2008.ꢀ
N.ꢀV.ꢀPlechkovaꢀandꢀK.ꢀR.ꢀSeddon,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2008,ꢀ
2
913-2924.ꢀ
3
2.ꢀ
M.ꢀ Gruttadauria,ꢀ F.ꢀ Giacalone,ꢀ P.ꢀ Loꢀ Meo,ꢀ A.ꢀ Mossutoꢀ
Marculescu,ꢀS.ꢀRielaꢀandꢀR.ꢀNoto,ꢀEur.ꢀJ.ꢀOrg.ꢀChem.,ꢀ2008,ꢀ
2
3
7,ꢀ123-150.ꢀ
2
008,ꢀ1589-1596.ꢀ
3
4
.ꢀ
.ꢀ
J.ꢀJ.ꢀH.ꢀDavis,ꢀChem.ꢀLett.,ꢀ2004,ꢀ33,ꢀ1072-1077.ꢀ
H.ꢀLi,ꢀB.ꢀWang,ꢀL.ꢀZhangꢀandꢀL.ꢀShen,ꢀJ.ꢀRadioanal.ꢀNucl.ꢀ
Chem.,ꢀ2015,ꢀ303,ꢀ433-440.ꢀ
3
3
3
3
3
3
3.ꢀ
4.ꢀ
5.ꢀ
6.ꢀ
7.ꢀ
8.ꢀ
M.ꢀ Lombardo,ꢀ E.ꢀ Montroni,ꢀ A.ꢀ Quintavallaꢀ andꢀ C.ꢀ
Trombini,ꢀAdv.ꢀSynth.ꢀCatal.,ꢀ2012,ꢀ354,ꢀ3428-3434.ꢀ
E.ꢀ Machuca,ꢀ G.ꢀ Granados,ꢀ B.ꢀ Hinojosaꢀ andꢀ E.ꢀ Juaristi,ꢀ
TetrahedronꢀLett.,ꢀ2015,ꢀ56,ꢀ6047-6051.ꢀ
A.ꢀ Psarra,ꢀ C.ꢀ G.ꢀ Kokotosꢀ andꢀ P.ꢀ Moutevelis-Minakakis,ꢀ
Tetrahedron,ꢀ2014,ꢀ70,ꢀ608-615.ꢀ
M.ꢀ Yoshida,ꢀ H.ꢀ Ukigai,ꢀ K.ꢀ Shibatomiꢀ andꢀ S.ꢀ Hara,ꢀ
TetrahedronꢀLett.,ꢀ2015,ꢀ56,ꢀ3890-3893.ꢀ
C.ꢀ Bonnot,ꢀ J.-C.ꢀ Chambron,ꢀ E.ꢀ Espinosa,ꢀ K.ꢀ Bernauer,ꢀ U.ꢀ
ScholtenꢀandꢀR.ꢀGraff,ꢀJ.ꢀOrg.ꢀChem.,ꢀ2008,ꢀ73,ꢀ7871-7881.ꢀ
L.ꢀYue,ꢀW.ꢀDu,ꢀY.-K.ꢀLiuꢀandꢀY.-C.ꢀChen,ꢀTetrahedronꢀLett.,ꢀ
5
6
.ꢀ
.ꢀ
C.ꢀ Chiappeꢀ andꢀ C.ꢀ S.ꢀ Pomelli,ꢀ Eur.ꢀ J.ꢀ Org.ꢀ Chem.,ꢀ 2014,ꢀ
2
014,ꢀ6120-6139.ꢀ
Z.ꢀFei,ꢀD.ꢀZhao,ꢀD.ꢀPieraccini,ꢀW.ꢀH.ꢀAng,ꢀT.ꢀJ.ꢀGeldbach,ꢀR.ꢀ
Scopelliti,ꢀ C.ꢀ Chiappeꢀ andꢀ P.ꢀ J.ꢀ Dyson,ꢀ Organometallics,ꢀ
2
007,ꢀ26,ꢀ1588-1598.ꢀ
7
8
.ꢀ
.ꢀ
D.ꢀZhao,ꢀZ.ꢀFei,ꢀT.ꢀJ.ꢀGeldbach,ꢀR.ꢀScopellitiꢀandꢀP.ꢀJ.ꢀDyson,ꢀ
J.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2004,ꢀ126,ꢀ15876-15882.ꢀ
J.ꢀLiu,ꢀH.ꢀLiuꢀandꢀL.ꢀWang,ꢀAppl.ꢀOrganomet.ꢀChem.,ꢀ2010,ꢀ
2
4,ꢀ386-391.ꢀ
2
008,ꢀ49,ꢀ3881-3884.ꢀ
8
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 9 of 11
Please Rꢀ d So Cꢀ n oA t dꢀ av da j nu cs teꢀ ms arginsꢀ
JournalꢀNameꢀ
ꢀARTICLEꢀ
3
4
4
4
4
4
4
9.ꢀ
0.ꢀ
1.ꢀ
2.ꢀ
3.ꢀ
4.ꢀ
5.ꢀ
F.ꢀD'Anna,ꢀV.ꢀFrenna,ꢀR.ꢀNoto,ꢀV.ꢀPaceꢀandꢀD.ꢀSpinelli,ꢀJ.ꢀ
Org.ꢀChem.,ꢀ2005,ꢀ70,ꢀ2828-2831.ꢀ
F.ꢀD'Anna,ꢀV.ꢀFrenna,ꢀV.ꢀPaceꢀandꢀR.ꢀNoto,ꢀTetrahedron,ꢀ
View Article Online
DOI: 10.1039/C6RA12037G
2
006,ꢀ62,ꢀ1690-1698.ꢀ
F.ꢀD'Anna,ꢀV.ꢀFrenna,ꢀS.ꢀLaꢀMarca,ꢀR.ꢀNoto,ꢀV.ꢀPaceꢀandꢀD.ꢀ
Spinelli,ꢀTetrahedron,ꢀ2008,ꢀ64,ꢀ672-680.ꢀ
J.ꢀA.ꢀCastro-Osma,ꢀJ.ꢀW.ꢀComerford,ꢀS.ꢀHeath,ꢀO.ꢀJones,ꢀM.ꢀ
MorcilloꢀandꢀM.ꢀNorth,ꢀRSCꢀAdv.,ꢀ2015,ꢀ5,ꢀ3678-3685.ꢀ
W.ꢀYang,ꢀY.ꢀJiaꢀandꢀD.-M.ꢀDu,ꢀOrg.ꢀBiomol.ꢀChem.,ꢀ2012,ꢀ
1
0,ꢀ332-338.ꢀ
M.ꢀ Fan,ꢀ J.ꢀ Yang,ꢀ P.ꢀ Jiang,ꢀ P.ꢀ Zhangꢀ andꢀ S.ꢀ Li,ꢀ RSCꢀ Adv.,ꢀ
013,ꢀ3,ꢀ752-756.ꢀ
Z.ꢀ Wang,ꢀ Q.ꢀ Wang,ꢀ Y.ꢀ Zhangꢀ andꢀ W.ꢀ Bao,ꢀ Tetrahedronꢀ
2
Lett.,ꢀ
2005,ꢀ
46,ꢀ
4657-4660.
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ9ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Please Rꢀ d So Cꢀ n oA t dꢀ av da j nu cs teꢀ ms arginsꢀ
Page 10 of 11
View Article Online
DOI: 10.1039/C6RA12037G
JournalꢀNameꢀ
ꢀ
ARTICLEꢀ
TableꢀofꢀContentsꢀ
Functionalisedꢀdiimidazoliumꢀsalts:ꢀtheꢀanionꢀeffectꢀonꢀtheꢀcatalyticꢀabilityꢀꢀꢀ
ꢀ
ꢀ
CarlaꢀRizzo,ꢀFrancescaꢀD’Anna*ꢀandꢀRenatoꢀNoto
ꢀ
ꢀ
ꢀ
or" 2"
ꢀ
ꢀ
ꢀ
=
"chiral"and"achiral"monoanions"
ꢀ
ꢀ
="chiral"and"achiral"dianions"
Howꢀ isꢀ itꢀ possibleꢀ toꢀ catalyzeꢀ andꢀ simultaneouslyꢀ controlꢀ theꢀ outcomeꢀ ofꢀ aꢀ reaction?ꢀ Employingꢀ taskꢀ specificꢀ ionicꢀ liquidsꢀ andꢀ
changingꢀtheirꢀanions.ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ10ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 11 of 11
RSC Advances
View Article Online
DOI: 10.1039/C6RA12037G
1
11x39mm (72 x 72 DPI)