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Page 4 of 4
COMMUNICATIONꢀ
JournalꢀNameꢀ
atoms,ꢀ whileꢀ thoseꢀ forꢀ 1.HBꢀ areꢀ muchꢀ broader,ꢀ spreadingꢀ Psychiatry,ꢀ2003,ꢀ5,ꢀ70-73.ꢀ
acrossꢀ theꢀ bindingꢀ sites.ꢀ Indeed,ꢀ theꢀ C–I···Oꢀ anglesꢀ inꢀ 1.XBꢀ 2.ꢀ G.ꢀWu,ꢀAdvꢀNutr,ꢀ2010,ꢀ1,ꢀ31-37.ꢀ
DOI: 10.1039/C6CC01701K
complexes,ꢀ rangingꢀ fromꢀ 169.3ꢀ toꢀ 177.7°,ꢀ showꢀ thatꢀ theꢀ XBꢀ 3.ꢀ W.ꢀH.ꢀPirkleꢀandꢀT.ꢀC.ꢀPochapsky,ꢀChem.ꢀRev.,ꢀ1989,ꢀ89,ꢀ347-362.ꢀ
interactionsꢀareꢀhighlyꢀdirectional,ꢀwhileꢀtheꢀC–H···Oꢀanglesꢀinꢀ 4.ꢀ V.ꢀSundaresanꢀandꢀR.ꢀAbrol,ꢀChirality,ꢀ2005,ꢀ17ꢀSuppl,ꢀS30-39.ꢀ
theꢀ complexesꢀ ofꢀ 1.HB,ꢀ varyingꢀ betweenꢀ 101.5ꢀ andꢀ 167.9°,ꢀ 5.ꢀ (a)ꢀS.ꢀKubik,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2009,ꢀ38,ꢀ585-605;ꢀ(b)ꢀL.ꢀPu,ꢀAcc.ꢀ
deviateꢀsignificantlyꢀfromꢀlinearityꢀ(seeꢀESIꢀTableꢀS5-2).ꢀTheseꢀ
importantꢀdifferencesꢀinꢀdirectionalityꢀbetweenꢀXBꢀandꢀHBꢀmayꢀ
accountꢀ forꢀ theꢀ enhancedꢀ enantioselectivityꢀ shownꢀ byꢀ 1.XBꢀ
overꢀ1.HB.ꢀ
Chem.ꢀRes.,ꢀ2012,ꢀ45,ꢀ150-163;ꢀ(c)ꢀF.ꢀUlatowskiꢀandꢀJ.ꢀJurczak,ꢀJ.ꢀ
Org.ꢀ Chem.,ꢀ 2015,ꢀ 80,ꢀ 4235-4243;ꢀ (d)ꢀ J.ꢀ M.ꢀ Grandaꢀ andꢀ J.ꢀ
Jurczak,ꢀChem.ꢀEur.ꢀJ.,ꢀ2015,ꢀ21,ꢀ16585-16592.ꢀ
6.ꢀ (a)ꢀT.ꢀEma,ꢀK.ꢀOkuda,ꢀS.ꢀWatanabe,ꢀT.ꢀYamasaki,ꢀT.ꢀMinami,ꢀN.ꢀA.ꢀ
Esipenkoꢀ andꢀ P.ꢀ Anzenbacher,ꢀ Jr.,ꢀ Org.ꢀ Lett.,ꢀ 2014,ꢀ 16,ꢀ 1302-
1
3
305;ꢀ (b)ꢀ H.ꢀ Itoꢀ andꢀ S.ꢀ Shinoda,ꢀ Chem.ꢀ Commun.,ꢀ 2015,ꢀ 51,ꢀ
808-3811.ꢀ
7
8
.ꢀ (a)ꢀM.ꢀMahlauꢀandꢀB.ꢀList,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀEngl.,ꢀ2013,ꢀ52,ꢀ
18-533;ꢀ(b)ꢀK.ꢀBrakꢀandꢀE.ꢀN.ꢀJacobsen,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀ
Engl.,ꢀ2013,ꢀ52,ꢀ534-561;ꢀ(c)ꢀR.ꢀJ.ꢀPhipps,ꢀG.ꢀL.ꢀHamiltonꢀandꢀF.ꢀD.ꢀ
Toste,ꢀNatꢀChem,ꢀ2012,ꢀ4,ꢀ603-614.ꢀ
.ꢀ (a)ꢀS.ꢀW.ꢀRobinson,ꢀC.ꢀL.ꢀMustoe,ꢀN.ꢀG.ꢀWhite,ꢀA.ꢀBrown,ꢀA.ꢀL.ꢀ
Thompson,ꢀ P.ꢀ Kennepohlꢀ andꢀ P.ꢀ D.ꢀ Beer,ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.,ꢀ
5
2
015,ꢀ 137,ꢀ 499-507;ꢀ (b)ꢀ Lydiaꢀ C.ꢀ Gilday,ꢀ Seanꢀ W.ꢀ Robinson,ꢀ
ꢀ
TimothyꢀA.ꢀBarendt,ꢀMatthewꢀJ.ꢀLangton,ꢀBenjaminꢀR.ꢀMullaneyꢀ
andꢀPaulꢀD.ꢀBeer,ꢀChem.ꢀRev.,ꢀ2015,ꢀ115,ꢀ7118-7195.ꢀ
.ꢀ M.ꢀ J.ꢀ Langton,ꢀ S.ꢀ W.ꢀ Robinson,ꢀ I.ꢀ Marques,ꢀ V.ꢀ Félixꢀ andꢀ P.ꢀ D.ꢀ
Beer,ꢀNatꢀChem,ꢀ2014,ꢀ6,ꢀ1039-1043.ꢀ
Fig.ꢀ3.ꢀDFTꢀoptimisedꢀstructuresꢀforꢀcomplexesꢀofꢀNBoc-(S)-tryptophanꢀwithꢀ1.XBꢀ
(left)ꢀandꢀ1.HBꢀ(right).ꢀTheꢀXBꢀandꢀHBꢀinteractionsꢀareꢀdepictedꢀasꢀpurpleꢀandꢀ
lightꢀblueꢀdashedꢀlines,ꢀrespectively.ꢀ
9
1
ꢀ
TheꢀdegreeꢀofꢀcovalencyꢀofꢀtheꢀXBꢀandꢀHBꢀinteractionsꢀwithꢀ
0.ꢀ(a)ꢀJ.ꢀY.ꢀLimꢀandꢀP.ꢀD.ꢀBeer,ꢀChem.ꢀCommun.,ꢀ2015,ꢀ51,ꢀ3686-
theꢀanionsꢀwasꢀassessedꢀusingꢀWibergꢀBondꢀIndicesꢀ(WBI,ꢀseeꢀ
ESI,ꢀTableꢀS5-3ꢀandꢀSectionꢀS6.9).ꢀTheꢀWBIꢀvaluesꢀforꢀtheꢀXBꢀ
interactionsꢀ rangeꢀ betweenꢀ 0.24ꢀ andꢀ 0.33,ꢀ whileꢀ forꢀ theꢀ HBꢀ
onesꢀ theseꢀ valuesꢀ areꢀ muchꢀ lower,ꢀ fromꢀ 0.03ꢀ toꢀ 0.07.ꢀ Theꢀ
linearityꢀ ofꢀ theꢀ XBꢀ interactions,ꢀ alongꢀ withꢀ aꢀ highꢀ degreeꢀ ofꢀ
covalency,ꢀ leadsꢀ toꢀ aꢀ higherꢀ bindingꢀ affinityꢀ ofꢀ 1.XBꢀ towardsꢀ
theꢀchiralꢀoxoanionsꢀwhenꢀcomparedꢀwithꢀ1.HB.ꢀ
3
688;ꢀ(b)ꢀC.ꢀJ.ꢀMassena,ꢀA.ꢀM.ꢀRiel,ꢀG.ꢀF.ꢀNeuhaus,ꢀD.ꢀA.ꢀDecatoꢀ
andꢀO.ꢀB.ꢀBerryman,ꢀChem.ꢀCommun.,ꢀ2015,ꢀ51,ꢀ1417-1420.ꢀ
1.ꢀ(a)ꢀY.ꢀWillener,ꢀK.ꢀM.ꢀJoly,ꢀC.ꢀJ.ꢀMoodyꢀandꢀJ.ꢀH.ꢀTucker,ꢀJ.ꢀOrg.ꢀ
Chem.,ꢀ 2008,ꢀ 73,ꢀ 1225-1233;ꢀ (b)ꢀ P.ꢀ Laurent,ꢀ H.ꢀ Miyaji,ꢀ S.ꢀ R.ꢀ
Collinson,ꢀ I.ꢀ Prokes,ꢀ C.ꢀ J.ꢀ Moody,ꢀ J.ꢀ H.ꢀ R.ꢀ Tuckerꢀ andꢀ A.ꢀ M.ꢀ Z.ꢀ
Slawin,ꢀOrg.ꢀLett.,ꢀ2002,ꢀ4,ꢀ4037-4040;ꢀ(c)ꢀG.ꢀMirri,ꢀS.ꢀD.ꢀBull,ꢀP.ꢀ
N.ꢀHorton,ꢀT.ꢀD.ꢀJames,ꢀL.ꢀMaleꢀandꢀJ.ꢀH.ꢀTucker,ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.,ꢀ 2010,ꢀ 132,ꢀ 8903-8905;ꢀ (d)ꢀ A.ꢀ Mulas,ꢀ Y.ꢀ Willener,ꢀ J.ꢀ Carr-
Smith,ꢀ K.ꢀ M.ꢀ Joly,ꢀ L.ꢀ Male,ꢀ C.ꢀ J.ꢀ Moody,ꢀ S.ꢀ L.ꢀ Horswell,ꢀ H.ꢀ V.ꢀ
NguyenꢀandꢀJ.ꢀH.ꢀTucker,ꢀDaltonꢀtransactions,ꢀ2015,ꢀ44,ꢀ7268-
7275.ꢀ
1
ꢀ
Inꢀconclusion,ꢀtheꢀfirstꢀchiralꢀXBꢀreceptorsꢀwereꢀsynthesisedꢀ
andꢀ shownꢀ toꢀ significantlyꢀ enhanceꢀ enantioselectiveꢀ anionꢀ
bindingꢀ andꢀ electrochemicalꢀ sensingꢀ behaviourꢀ comparedꢀ toꢀ
theirꢀproticꢀanalogues.ꢀComputationalꢀmodellingꢀindicatesꢀthatꢀ
theꢀstrictꢀlinearityꢀofꢀXBꢀandꢀhost-guestꢀstericꢀinteractionsꢀplayꢀ 12.ꢀK.ꢀBurglova,ꢀN.ꢀMoitra,ꢀJ.ꢀHodacova,ꢀX.ꢀCattoenꢀandꢀM.ꢀW.ꢀMan,ꢀ
J.ꢀOrg.ꢀChem.,ꢀ2011,ꢀ76,ꢀ7326-7333.ꢀ
3.ꢀW.ꢀS.ꢀBrotherton,ꢀR.ꢀJ.ꢀClarkꢀandꢀL.ꢀZhu,ꢀJ.ꢀOrg.ꢀChem.,ꢀ2012,ꢀ77,ꢀ
dominantꢀrolesꢀinꢀtheꢀenhancedꢀchiralꢀrecognitionꢀbehaviour.ꢀ
Theꢀexploitationꢀofꢀhalogenꢀbondingꢀforꢀchiralꢀrecognitionꢀandꢀ
analyteꢀsensingꢀisꢀcontinuingꢀinꢀourꢀlaboratories.ꢀ
1
1
6
443-6455.ꢀ
4.ꢀD.ꢀ Parmar,ꢀ E.ꢀ Sugiono,ꢀ S.ꢀ Rajaꢀ andꢀ M.ꢀ Rueping,ꢀ Chem.ꢀ Rev.,ꢀ
014,ꢀ114,ꢀ9047-9153.ꢀ
ꢀ
J.ꢀ Y.ꢀ C.ꢀ Limꢀ thanksꢀ A*STAR,ꢀ Singapore,ꢀ forꢀ aꢀ postgraduateꢀ
2
scholarship.ꢀTheꢀtheoreticalꢀstudiesꢀwereꢀcarriedꢀoutꢀwithinꢀtheꢀ
scopeꢀofꢀtheꢀprojectsꢀiBiMEDꢀ–ꢀInstituteꢀofꢀBiomedicineꢀ(FCTꢀRef.ꢀ
UID/BIM/04501/2013),ꢀ andꢀ CICECOꢀ –ꢀ Aveiroꢀ Instituteꢀ ofꢀ
Materialsꢀ(FCTꢀRef.ꢀUID/CTM/50011/2013),ꢀfinancedꢀbyꢀnationalꢀ
fundsꢀthroughꢀtheꢀFCT/MECꢀandꢀwhenꢀappropriateꢀco-financedꢀ
byꢀFEDERꢀunderꢀtheꢀCOMPETE2020ꢀProgrammeꢀandꢀtheꢀPT2020ꢀ
Partnershipꢀ Agreement.ꢀ I.M.ꢀ thanksꢀ theꢀ FCTꢀ forꢀ theꢀ PhDꢀ
scholarshipꢀ SFRH/BD/87520/2012.ꢀ L.F.ꢀ thanksꢀ FCTꢀ forꢀ aꢀ grantꢀ
withinꢀtheꢀprojectꢀANR/IMI-MIC/0041/2012.ꢀ
1
1
5.ꢀM.ꢀJ.ꢀHynes,ꢀJꢀChemꢀSocꢀDalton,ꢀ1993,ꢀ311-312.ꢀ
6.ꢀKratochv.B,ꢀE.ꢀLorahꢀandꢀC.ꢀGarber,ꢀAnal.ꢀChem.,ꢀ1969,ꢀ41,ꢀ1793-
1
796.ꢀ
1
7.ꢀD.ꢀ A.ꢀ Case,ꢀ V.ꢀ Babin,ꢀ J.ꢀ T.ꢀ Berryman,ꢀ R.ꢀ M.ꢀ Betz,ꢀ Q.ꢀ Cai,ꢀ D.ꢀ S.ꢀ
Cerutti,ꢀI.ꢀT.ꢀE.ꢀCheatham,ꢀT.ꢀA.ꢀDarden,ꢀR.ꢀE.ꢀDuke,ꢀH.ꢀGohlke,ꢀA.ꢀ
W.ꢀ Goetz,ꢀ S.ꢀ Gusarov,ꢀ N.ꢀ Homeyer,ꢀ P.ꢀ Janowski,ꢀ J.ꢀ Kaus,ꢀ I.ꢀ
Kolossváry,ꢀ A.ꢀ Kovalenko,ꢀ T.ꢀ S.ꢀ Lee,ꢀ S.ꢀ LeGrand,ꢀ T.ꢀ Luchko,ꢀ R.ꢀ
Luo,ꢀB.ꢀMadej,ꢀK.ꢀM.ꢀMerz,ꢀF.ꢀPaesani,ꢀD.ꢀR.ꢀRoe,ꢀA.ꢀRoitberg,ꢀC.ꢀ
Sagui,ꢀR.ꢀSalomon-Ferrer,ꢀG.ꢀSeabra,ꢀC.ꢀL.ꢀSimmerling,ꢀW.ꢀSmith,ꢀ
J.ꢀ Swails,ꢀ R.ꢀ C.ꢀ Walker,ꢀ J.ꢀ Wang,ꢀ R.ꢀ M.ꢀ Wolf,ꢀ X.ꢀ Wuꢀ andꢀ P.ꢀ A.ꢀ
Kollman,ꢀ AMBERꢀ 14,ꢀ (2014)ꢀ Universityꢀ ofꢀ California,ꢀ Sanꢀ
Francisco.ꢀ
8.ꢀ(a)ꢀJ.ꢀWang,ꢀR.ꢀM.ꢀWolf,ꢀJ.ꢀW.ꢀCaldwell,ꢀP.ꢀA.ꢀKollmanꢀandꢀD.ꢀA.ꢀ
Case,ꢀJ.ꢀComput.ꢀChem.,ꢀ2004,ꢀ25,ꢀ1157-1174;ꢀ(b)ꢀJ.ꢀWang,ꢀR.ꢀM.ꢀ
Wolf,ꢀJ.ꢀW.ꢀCaldwell,ꢀP.ꢀA.ꢀKollmanꢀandꢀD.ꢀA.ꢀCase,ꢀJ.ꢀComput.ꢀ
Chem.,ꢀ2005,ꢀ26,ꢀ114-114.ꢀ
Notesꢀandꢀreferencesꢀ
†
ꢀ Methoxy-protectedꢀBINOLꢀreceptorsꢀwereꢀusedꢀforꢀthisꢀstudyꢀ
asꢀ preliminaryꢀ bindingꢀ studiesꢀ usingꢀ freeꢀ BINOL-OHꢀ receptorsꢀ
resultedꢀ inꢀ deprotonationꢀ uponꢀ additionꢀ ofꢀ basicꢀ carboxylateꢀ
1
anionsꢀinꢀMeCN/H
ꢀ TheꢀassignmentꢀofꢀtheꢀaromaticꢀprotonꢀsignalsꢀofꢀtheꢀBINOLꢀ
coreꢀwasꢀperformedꢀusingꢀ1DꢀNOESYꢀexperimentsꢀ(ESI).ꢀ
ꢀ2.HBꢀshowedꢀpoorꢀelectrochemicalꢀreversibilityꢀwhichꢀnegatedꢀ
chiralꢀanionꢀsensingꢀexperimentsꢀbeingꢀundertakenꢀ(seeꢀESI).ꢀꢀ
|ꢀ NoꢀreliableꢀelectrochemicalꢀdataꢀcouldꢀbeꢀobtainedꢀforꢀNBoc-
2
Oꢀ99:1.ꢀ
§
1
2
9.ꢀM.ꢀA.ꢀIbrahim,ꢀJ.ꢀComput.ꢀChem.,ꢀ2011,ꢀ32,ꢀ2564-2574.ꢀ
0.ꢀS.ꢀM.ꢀMacDonaldꢀandꢀS.ꢀG.ꢀRoscoe,ꢀElectrochim.ꢀActa,ꢀ1997,ꢀ42,ꢀ
#
1
189-1200.ꢀ
|
20
tryptophanꢀdueꢀtoꢀoxidationꢀofꢀtheꢀindoleꢀmotif. ꢀ
4
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
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