Porous Rh/BINAP polymers as efficient heterogeneous catalysts for asymmetric hydroformylation of styrene: Enhanced enantioselectivity realized by flexible chiral nanopockets

Article abstract of DOI:10.1016/S1872-2067(17)62790-6

A new chiral monomer, (S)-5,5′-divinyl-BINAP, was successfully synthesized and embedded into two different porous organic polymers (Poly-1 and Poly-2). After loading a Rh species, the catalysts were applied for the heterogeneous asymmetric hydroformylation of styrene. Compared with the homogeneous BINAP analogue, the enantioselectivity of Rh/Poly-1 catalyst was drastically increased by approximately 70%. The improved enantioselectivity of the porous Rh/BINAP polymers was attributed to the presence of flexible chiral nanopockets resulting from the increased bulk of the R groups near the catalytic center.

Full text of DOI:10.1016/S1872-2067(17)62790-6

ChineseꢀJournalꢀofꢀCatalysisꢀ38ꢀ(2017)ꢀ691–698
ꢀ
ꢀ ꢀ ꢀ
ꢀ ꢀ ꢀ ꢀ
a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
ꢀ
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
ꢀ
ꢀ
Article
PorousꢀRh/BINAPꢀpolymersꢀasꢀefficientꢀheterogeneousꢀcatalystsꢀforꢀ
asymmetricꢀhydroformylationꢀofꢀstyrene:ꢀEnhancedꢀ ꢀ
enantioselectivityꢀrealizedꢀbyꢀflexibleꢀchiralꢀnanopocketsꢀ
a,b
a
a,#
c
a,b
d
TaoꢀWangꢀ ,ꢀWenlongꢀWangꢀ ,ꢀYuanꢀLyuꢀ ,ꢀKaiꢀXiongꢀ ,ꢀCunyaoꢀLiꢀ ,ꢀHaoꢀZhangꢀ ,ꢀ ꢀ
c
d
a,
ZhuangpingꢀZhanꢀ ,ꢀZhengꢀJiangꢀ ,ꢀYunjieꢀDingꢀ *
ꢀ
aꢀDalianꢀNationalꢀLaboratoryꢀforꢀCleanꢀEnergy,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences,ꢀDalianꢀ116023,ꢀLiaoning,ꢀChinaꢀ
bꢀUniversityꢀofꢀChineseꢀAcademyꢀofꢀSciences,ꢀBeijingꢀ100049,ꢀChinaꢀ
cꢀDepartmentꢀofꢀChemistry,ꢀXiamenꢀUniversity,ꢀXiamenꢀ361005,ꢀFujian,ꢀChinaꢀ
dꢀShanghaiꢀSynchrotronꢀRadiationꢀFacility,ꢀShanghaiꢀInstituteꢀofꢀAppliedꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences,ꢀShanghaiꢀ201204,ꢀChinaꢀ
A R T I C L E ꢀ I N F O ꢀ
A B S T R A C T ꢀ
Articleꢀhistory:ꢀ
Aꢀ newꢀ chiralꢀ monomer,ꢀ (S)‐5,5′‐divinyl‐BINAP,ꢀ wasꢀ successfullyꢀ synthesizedꢀ andꢀ embeddedꢀ intoꢀ
twoꢀdifferentꢀporousꢀorganicꢀpolymersꢀ(Poly‐1ꢀandꢀPoly‐2).ꢀAfterꢀloadingꢀaꢀRhꢀspecies,ꢀtheꢀcatalystsꢀ
wereꢀappliedꢀforꢀtheꢀheterogeneousꢀasymmetricꢀhydroformylationꢀofꢀstyrene.ꢀComparedꢀwithꢀtheꢀ
homogeneousꢀ BINAPꢀ analogue,ꢀ theꢀ enantioselectivityꢀ ofꢀ Rh/Poly‐1ꢀ catalystꢀ wasꢀ drasticallyꢀ in‐
creasedꢀbyꢀapproximatelyꢀ70%.ꢀTheꢀimprovedꢀenantioselectivityꢀofꢀtheꢀporousꢀRh/BINAPꢀpolymersꢀ
wasꢀattributedꢀtoꢀtheꢀpresenceꢀofꢀflexibleꢀchiralꢀnanopocketsꢀresultingꢀfromꢀtheꢀincreasedꢀbulkꢀofꢀ
theꢀRꢀgroupsꢀnearꢀtheꢀcatalyticꢀcenter.ꢀ
Receivedꢀ15ꢀDecemberꢀ2016ꢀ
Acceptedꢀ15ꢀJanuaryꢀ2017ꢀ
Publishedꢀ5ꢀAprilꢀ2017ꢀ
Keywords:ꢀ
Porousꢀorganicꢀpolymerꢀ
Heterogeneousꢀcatalysisꢀ
Asymmetricꢀhydroformylationꢀ
Enhancedꢀenatioselectivityꢀ
Chiralꢀnanopocket
©ꢀ2017,ꢀDalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChineseꢀAcademyꢀofꢀSciences.
PublishedꢀbyꢀElsevierꢀB.V.ꢀAllꢀrightsꢀreserved.
1.ꢀ ꢀ Introductionꢀ
resultsꢀhaveꢀbeenꢀreportedꢀ[2–5].ꢀForꢀexample,ꢀNozakiꢀetꢀal.ꢀ[6]ꢀ
developedꢀ theꢀ chiralꢀ phosphine–phosphiteꢀ ligandꢀ (R,S)‐
ꢀꢀ
Asymmetricꢀhydroformylationꢀ isꢀoneꢀofꢀtheꢀmostꢀversatileꢀ
BINAPHOS;ꢀ hydroformylationꢀ ofꢀ styreneꢀ withꢀ highꢀ enantiose‐
lectivityꢀwasꢀachievedꢀ(upꢀtoꢀ94%ꢀee,ꢀiso/normalꢀ=ꢀ7.3)ꢀbyꢀus‐
ingꢀ Rhꢀ complexesꢀ ofꢀ thisꢀ newꢀ ligand.ꢀ However,ꢀ althoughꢀ di‐
phosphineꢀ ligandsꢀ showꢀ excellentꢀ catalyticꢀ activitiesꢀ inꢀ asym‐
metricꢀhydrogenation,ꢀtheyꢀalwaysꢀleadꢀtoꢀdisappointingꢀresultsꢀ
inꢀasymmetricꢀhydroformylationꢀofꢀstyreneꢀ[7,8].ꢀAnꢀeeꢀvalueꢀofꢀ
60%ꢀhasꢀbeenꢀobtainedꢀinꢀaꢀRh‐diphosphineꢀsystemꢀbyꢀusingꢀaꢀ
chiralꢀ BDPPꢀ ligandꢀ [9].ꢀ Otherꢀ diphosphinesꢀ suchꢀ asꢀ DIOP,ꢀ
TREDIPꢀ andꢀ CHRAPHOSꢀ giveꢀ lowꢀ enantioselectivitiesꢀ ofꢀ lessꢀ
thanꢀ30%ꢀ[8–11].ꢀBINAPꢀligand,ꢀwhichꢀisꢀunambiguouslyꢀoneꢀofꢀ
methodsꢀforꢀtheꢀsynthesisꢀofꢀenantiomericallyꢀpureꢀcompoundsꢀ
suchꢀasꢀopticallyꢀactiveꢀaldehydes,ꢀα‐aminoꢀacidsꢀandꢀalcohols.ꢀ
Althoughꢀ itꢀ hasꢀ beenꢀ researchedꢀ forꢀ moreꢀ thanꢀ 40ꢀ years,ꢀ
asymmetricꢀ hydroformylationꢀ withꢀ goodꢀ enantioselectivity,ꢀ
chemoselectivityꢀandꢀregioselectivityꢀisꢀstillꢀaꢀchallengeꢀinꢀtheꢀ
fieldꢀofꢀcatalysisꢀandꢀfineꢀchemicalꢀsynthesisꢀ[1].ꢀ ꢀ
Soꢀ far,ꢀ Rhꢀ catalystsꢀ associatedꢀ toꢀ chiralꢀ phosphine–phos‐
ꢀ
phiteꢀligandsꢀorꢀdiphosphiteꢀligandsꢀareꢀtheꢀmostꢀstudiedꢀsys‐
temsꢀ inꢀ asymmetricꢀ hydroformylation,ꢀ andꢀ someꢀ satisfactoryꢀ
*
ꢀ
ꢀCorrespondingꢀauthor.ꢀTel:ꢀ+86‐411‐84379143;ꢀFax:ꢀ+86‐411‐84379143;ꢀE‐mail:ꢀdyj@dicp.ac.cnꢀ
Correspondingꢀauthor.ꢀTel:ꢀ+86‐411‐84379601;ꢀFax:ꢀ+86‐411‐84379143;ꢀE‐mail:ꢀluyuan@dicp.ac.cn
#
ThisꢀworkꢀwasꢀsupportedꢀbyꢀtheꢀStrategicꢀpriorityꢀResearchꢀProgramꢀofꢀtheꢀChineseꢀAcademyꢀofꢀSciencesꢀ(XDB17020400).ꢀ
DOI:ꢀ10.1016/S1872‐2067(17)62790‐6|ꢀhttp://www.sciencedirect.com/science/journal/18722067ꢀ|ꢀChin.ꢀJ.ꢀCatal.,ꢀVol.ꢀ38,ꢀNo.ꢀ4,ꢀAprilꢀ2017ꢀ ꢀ ꢀ

692ꢀ
TaoꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ38ꢀ(2017)ꢀ691–698ꢀ
Schemeꢀ1.ꢀSynthesisꢀofꢀ5,5’‐divinyl‐BINAP.ꢀ
theꢀ mostꢀ prominentꢀ chiralꢀ ligandsꢀ forꢀ asymmetricꢀ catalysisꢀ
12–14],ꢀonlyꢀexhibitsꢀanꢀeeꢀvalueꢀofꢀ25%ꢀwhenꢀcombinedꢀwithꢀ
heterogeneousꢀ hydroformylationꢀ catalystsꢀ preparedꢀ byꢀ theꢀ
copolymerizationꢀofꢀvinyl‐functionalizedꢀPPh
ꢀwithꢀvinyl‐func‐
[
3
ꢀ
Rhꢀspeciesꢀforꢀtheꢀasymmetricꢀhydroformylationꢀofꢀstyreneꢀ[9].ꢀ
Manyꢀ modifiedꢀ structuresꢀ ofꢀ BINAPꢀ haveꢀ beenꢀ preparedꢀ toꢀ
increaseꢀtheꢀefficiencyꢀorꢀenantioselectivityꢀofꢀasymmetricꢀhy‐
tionalizedꢀbiphephosꢀligandꢀ[31,32].ꢀMoreꢀimportantly,ꢀXiaoꢀetꢀ
al.ꢀ [33]ꢀ synthesizedꢀ chiralꢀ porousꢀ cross‐linkedꢀ polymersꢀ
(PCP‐BINAP)ꢀunderꢀsolvothermalꢀconditions.ꢀPCP‐BINAPOꢀwasꢀ
firstꢀobtainedꢀthroughꢀtheꢀcopolymerizationꢀofꢀdivinylbenzeneꢀ
andꢀ5,5’‐diacryloylaminoꢀBINAPꢀdioxide.ꢀThen,ꢀPCP‐BINAPꢀwasꢀ
drogenationꢀ[15].ꢀLinꢀetꢀal.ꢀ[16]ꢀdevelopedꢀaꢀfamilyꢀofꢀ4,4’‐sub‐
ꢀ
stitutedꢀ BINAPꢀ derivativesꢀ forꢀ asymmetricꢀ hydrogenationꢀ ofꢀ
ethylꢀbenzoylacetate.ꢀTheꢀRuꢀcatalystsꢀbasedꢀonꢀbulkyꢀsubstit‐
uentsꢀofꢀBINAP,ꢀsuchꢀasꢀtrimethylsilane,ꢀdiphenylmethanolꢀandꢀ
synthesizedꢀbyꢀtheꢀreductionꢀofꢀPCP‐BINAPOꢀwithꢀHSiCl .ꢀTheꢀ
3
preparedꢀRu/PCP‐BINAPꢀcatalystꢀexhibitedꢀhighꢀactivity,ꢀexcel‐
lentꢀ enantioselectivity,ꢀ andꢀ extraordinaryꢀ recyclabilityꢀ inꢀ
asymmetricꢀhydrogenationꢀofꢀβ‐ketoꢀesters.ꢀ ꢀ
InspiredꢀbyꢀXiao’sꢀwork,ꢀinꢀthisꢀpaperꢀweꢀalsoꢀreportꢀaꢀvi‐
nyl‐modifiedꢀ BINAP,ꢀ (S)‐5,5’‐divinyl‐BINAP,ꢀ andꢀ itsꢀ corre‐
spondingꢀporousꢀorganicꢀpolymersꢀaffordedꢀbyꢀtheꢀcopolymer‐
1‐cyclopentanol,ꢀprovidedꢀeeꢀvaluesꢀofꢀmoreꢀthanꢀ99%.ꢀWhenꢀ
usingꢀrelativelyꢀsmallꢀsubstituents,ꢀsuchꢀasꢀmethylꢀandꢀphenyl,ꢀ
theꢀcatalystsꢀprovidedꢀeeꢀvaluesꢀofꢀlessꢀthanꢀ87%.ꢀRemarkably,ꢀ
theꢀenantioselectivityꢀwasꢀ dramaticallyꢀenhancedꢀ whenꢀ bulkyꢀ
groupsꢀ wereꢀ introducedꢀ atꢀ theꢀ 4,4’‐positionsꢀ ofꢀ BINAP.ꢀ Theꢀ
reasonꢀcouldꢀbeꢀexplainedꢀbyꢀtheꢀsignificantꢀrepulsiveꢀinterac‐
tionsꢀbetweenꢀtheꢀbulkyꢀsubstituentsꢀofꢀBINAPꢀandꢀtheꢀphenylꢀ
groupꢀofꢀtheꢀ substrate,ꢀwhichꢀ resultsꢀinꢀdestabilizationꢀofꢀtheꢀ
disfavoredꢀtransitionꢀstate,ꢀandꢀthus,ꢀaꢀdramaticꢀenhancementꢀ
izationꢀ withꢀ divinylꢀ benzeneꢀ andꢀ 1,3,5‐tri(4‐
ꢀ
vinylphenyl)ben‐
ꢀ
zeneꢀ(Schemeꢀ1).ꢀLinearꢀethyleneꢀglycolꢀdimethacrylateꢀmon‐
omerꢀ wasꢀ alsoꢀ copolymerizedꢀ withꢀ divinyl‐modifiedꢀ BINAP;ꢀ
however,ꢀaꢀnonporousꢀmaterialꢀwasꢀobtainedꢀandꢀthisꢀmaterialꢀ
wasꢀintroducedꢀasꢀaꢀnegativeꢀcontrol.ꢀTheꢀBINAPꢀligandꢀwasꢀnotꢀ
onlyꢀ simplyꢀ incorporatedꢀ intoꢀ theꢀ polymers,ꢀ butꢀ canꢀ alsoꢀ beꢀ
ofꢀtheꢀenantioselectivity.ꢀTheseꢀligandsꢀwithꢀaꢀ“chiralꢀpocket”‐
ꢀ
likeꢀdesignꢀhaveꢀbeenꢀreportedꢀinꢀrecentꢀyearsꢀ[17–20].ꢀHow‐
ever,ꢀ BINAP‐basedꢀ ligandsꢀ haveꢀ rarelyꢀ beenꢀ reportedꢀ forꢀ hy‐
droformylationꢀreactionsꢀowingꢀtoꢀtheirꢀrelativelyꢀlowꢀenanti‐
oselectivity.ꢀ Consideringꢀ thatꢀ BINAPꢀ isꢀ oneꢀ ofꢀ theꢀ mostꢀ im‐
portantꢀ chiralꢀ ligands,ꢀ canꢀ beꢀ producedꢀ atꢀ anꢀ industrialꢀ scaleꢀ
andꢀhasꢀextensiveꢀapplicationsꢀinꢀasymmetricꢀcatalysis,ꢀmodi‐
fiedꢀ BINAP‐relatedꢀ catalystsꢀ forꢀ hydroformylationꢀ reactionsꢀ
deserveꢀfurtherꢀinvestigations.ꢀ
consideredꢀasꢀmodifiedꢀbyꢀbulkyꢀblocksꢀfromꢀotherꢀco‐mono‐
ꢀ
mersꢀorꢀBINAPꢀitself.ꢀThus,ꢀnumerousꢀhighlyꢀflexibleꢀnanopo‐
rousꢀ chiralꢀ pocketsꢀ wereꢀ presentꢀ inꢀ theꢀ polymerꢀ materialsꢀ
(Schemeꢀ2).ꢀAfterꢀloadingꢀwithꢀRhꢀspecies,ꢀtheꢀnanoporousꢀchi‐
ral‐pockets‐basedꢀ BINAPꢀ polymersꢀ shouldꢀ beꢀ veryꢀ favorableꢀ
forꢀtheꢀimprovementꢀofꢀtheꢀenantioselectivityꢀofꢀtheꢀasymmet‐
ricꢀhydroformylationꢀofꢀstyrene.ꢀToꢀdemonstrateꢀtheꢀ“proof‐of‐
ꢀ
Theꢀ disadvantagesꢀ ofꢀ homogeneousꢀ catalysis,ꢀ suchꢀ asꢀ theꢀ
wasteꢀofꢀexpensiveꢀtransitionꢀmetalꢀcomplexesꢀandꢀcontamina‐
tionꢀofꢀproducts,ꢀdroveꢀusꢀtoꢀexploreꢀmoreꢀpracticalꢀheteroge‐
neousꢀsystemsꢀ[21–24].ꢀTheꢀimmobilizationꢀofꢀorganometallicꢀ
complexesꢀontoꢀhighlyꢀporousꢀsolidsꢀisꢀstillꢀanꢀexcellentꢀstrate‐
gyꢀforꢀcombiningꢀtheꢀadvantagesꢀofꢀhomogeneousꢀandꢀhetero‐
geneousꢀ catalystsꢀ [25,26].ꢀ Amongꢀ variousꢀ porousꢀ supportingꢀ
materials,ꢀ porousꢀ organicꢀ polymers,ꢀ anꢀ emergingꢀ classꢀ ofꢀ po‐
rousꢀmaterials,ꢀcouldꢀbeꢀaꢀpromisingꢀcandidateꢀbecauseꢀofꢀtheirꢀ
highꢀsurfaceꢀareas,ꢀadvancedꢀhierarchicalꢀporeꢀstructuresꢀandꢀ
outstandingꢀstabilitiesꢀ[27,28].ꢀRecently,ꢀporousꢀpolymersꢀwithꢀ
excellentꢀ swellingꢀ propertiesꢀ wereꢀ preparedꢀ throughꢀ theꢀ
polymerizationꢀ ofꢀ vinyl‐functionalizedꢀ monomersꢀ underꢀ sol‐
vothermalꢀ conditionsꢀ [29,30].ꢀ Theꢀ swollenꢀ polymersꢀ canꢀ beꢀ
characterizedꢀasꢀaꢀsolutionꢀtoꢀaꢀcertainꢀdegree,ꢀalthoughꢀtheyꢀ
areꢀ elasticꢀ solidsꢀ ratherꢀ thanꢀ liquids;ꢀ thisꢀ liquid‐likeꢀ natureꢀ
endowsꢀ theꢀ polymersꢀ withꢀ surprisinglyꢀ highꢀ flexibility.ꢀ Evenꢀ
moreꢀimportant,ꢀitꢀhasꢀbeenꢀwellꢀrecognizedꢀthatꢀtheꢀflexibilityꢀ
ofꢀtheꢀactiveꢀsitesꢀinꢀsolidꢀcatalystsꢀplaysꢀaꢀveryꢀimportantꢀroleꢀ
inꢀtheꢀimprovementꢀofꢀtheꢀcatalyticꢀperformance.ꢀ
concept”,ꢀinꢀthisꢀcontribution,ꢀ twoꢀporousꢀpolymer‐supportedꢀ
Rh/BINAPꢀ catalystsꢀwereꢀ designedꢀ andꢀ synthesizedꢀ andꢀtheirꢀ
P
P
Co-monomer A, B or C
AIBN, THF, 100 oC, 24 h
PPh2
PPh2
Ph2P PPh2
chiral porket
P
P
O
O
Co-monomer
= Polymer
O
O
A
B
C
BINAP + A
Poly-1
BINAP + B
Poly-2
BINAP + C
Poly-3
P
Previously,ꢀ ourꢀ groupꢀ reportedꢀ aꢀ seriesꢀ ofꢀ highlyꢀ efficientꢀ
Schemeꢀ2.ꢀSynthesisꢀandꢀstructuresꢀofꢀPoly‐1,ꢀPoly‐2,ꢀandꢀPoly‐3.ꢀ

ꢀ
TaoꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ38ꢀ(2017)ꢀ691–698ꢀ
693ꢀ
catalyticꢀ performanceꢀ andꢀ recyclabilityꢀ wereꢀ investigatedꢀ forꢀ
theꢀheterogeneousꢀasymmetricꢀhydroformylationꢀofꢀstyrene.ꢀ
1H,ꢀJ
1
ꢀ=ꢀ10.9ꢀHz,ꢀJ
2
ꢀ=ꢀ1.6ꢀHz),ꢀ5.76ꢀ(dd,ꢀ1H,ꢀJ
1
ꢀ=ꢀ17.3ꢀHz,ꢀJ
2
ꢀ=ꢀ1.6ꢀ
Hz),ꢀ6.79ꢀ(d,ꢀ1H,ꢀJꢀ=ꢀ8.4ꢀHz),ꢀ6.85–6.90ꢀ(m,ꢀ1H),ꢀ7.05–7.17ꢀ(m,ꢀ
13
1
0H),ꢀ7.45–7.51ꢀ(m,ꢀ3H),ꢀ8.17ꢀ(d,ꢀ1H,ꢀJꢀ=ꢀ8.8ꢀHz);ꢀ CꢀNMRꢀ(100ꢀ
MHz,ꢀ CDCl )ꢀδꢀ 117.2,ꢀ 123.9,ꢀ 124.4,ꢀ125.5,ꢀ127.6,ꢀ 127.7,ꢀ128.0,ꢀ
28.4,ꢀ 130.7,ꢀ 130.9,ꢀ 132.8,ꢀ 132.9,ꢀ 133.0,ꢀ 133.5,ꢀ 134.1,ꢀ 134.2,ꢀ
2.ꢀ ꢀ Experimentalꢀ ꢀ
3
1
2.1.ꢀ ꢀ Materialsꢀ
134.3,ꢀ 134.5,ꢀ 135.4;ꢀ 31Pꢀ NMRꢀ (161ꢀ MHz,ꢀ CDCl
3
)ꢀ –15.7ꢀ Hz;ꢀ
+
44 6 2
HRMS(ESI):ꢀm/zꢀcalc.ꢀforꢀC48H O P ꢀ[M+H] :ꢀ675.2370,ꢀfound:ꢀ
Allꢀsolventsꢀwereꢀanalyticalꢀgradeꢀandꢀwereꢀpurifiedꢀbyꢀdis‐
675.2373.ꢀ
tillationꢀ underꢀ Arꢀ atmosphereꢀ beforeꢀ use.ꢀ Unlessꢀ otherwiseꢀ
noted,ꢀallꢀmanipulationsꢀwereꢀcarriedꢀoutꢀunderꢀanꢀArꢀatmos‐
phereꢀ eitherꢀ inꢀ aꢀ glove‐boxꢀ orꢀ usingꢀ standardꢀ Schlenkꢀ tech‐
niques.ꢀ
2.3.ꢀ ꢀ Synthesisꢀofꢀpolymersꢀ
Theseꢀ polymersꢀ wereꢀ preparedꢀ throughꢀ aꢀ free‐radicalꢀ
polymerizationꢀofꢀvinyl‐functionalizedꢀBINAPꢀligandꢀandꢀotherꢀ
co‐monomersꢀ inꢀ THFꢀ atꢀ 100ꢀ °C.ꢀ Inꢀ anꢀ autoclave,ꢀ 0.30ꢀ gꢀ ofꢀ
2.2.ꢀ ꢀ Synthesisꢀofꢀ(S)‐5,5’‐divinyl‐BINAPꢀ
(S)‐5,5’‐divinyl‐BINAPꢀ andꢀ 0.60ꢀ gꢀ ofꢀ divinylꢀ benzeneꢀ (DVB)ꢀ
2
.2.1.ꢀ ꢀ Synthesisꢀofꢀcompoundꢀ1,ꢀ(S)‐BINAPꢀdioxideꢀ ꢀ
(
wereꢀdissolvedꢀinꢀ9ꢀmLꢀofꢀtetrahydrofuranꢀ(THF),ꢀfollowedꢀbyꢀ
theꢀ additionꢀ ofꢀ 23ꢀ mgꢀ ofꢀ 2,2'‐azoisobutyronitrileꢀ (AIBN).ꢀ Theꢀ
mixtureꢀwasꢀfirstꢀstirredꢀforꢀ10ꢀminꢀatꢀtheꢀroomꢀtemperatureꢀ
andꢀthenꢀheatedꢀatꢀ100ꢀ°Cꢀforꢀ24ꢀh.ꢀTheꢀsolventꢀwasꢀremovedꢀ
underꢀvacuumꢀatꢀ65ꢀ°Cꢀandꢀaꢀwhiteꢀsolidꢀwasꢀobtained,ꢀwhichꢀ
wasꢀdenotedꢀasꢀPoly‐1.ꢀ ꢀ
S)‐BINAPꢀ (3ꢀ mmol,ꢀ 1.87ꢀ g)ꢀ wasꢀ dissolvedꢀ inꢀ dichloro‐
methaneꢀ(DCM,ꢀ60ꢀmL),ꢀfollowedꢀbyꢀdropwiseꢀadditionꢀofꢀH
18.32ꢀ mmol,ꢀ 6.06ꢀ mL).ꢀ Theꢀ reactionꢀ wasꢀ monitoredꢀ byꢀ
2 2
O ꢀ
(
thin‐layerꢀchromatographyꢀ(TLC).ꢀAfterꢀstirringꢀforꢀ30ꢀminꢀatꢀ
roomꢀtemperature,ꢀtheꢀsolutionꢀwasꢀextractedꢀwithꢀwaterꢀ(30ꢀ
mL).ꢀTheꢀorganicꢀphaseꢀwasꢀwashedꢀwithꢀ10%ꢀNaHSO
3
ꢀaque‐
Poly‐2ꢀwasꢀobtainedꢀusingꢀtheꢀsameꢀsynthesisꢀmethodꢀbutꢀ
usingꢀ0.60ꢀgꢀofꢀ1,3,5‐tri(4‐vinylphenyl)benzeneꢀinsteadꢀofꢀ0.60ꢀ
gꢀDVB.ꢀ ꢀ
ousꢀsolutionꢀ(50ꢀmL)ꢀandꢀdriedꢀoverꢀNa SO .ꢀTheꢀsolventꢀwasꢀ
2
4
removedꢀ underꢀ vacuumꢀ andꢀ (S)‐BINAPOꢀ wasꢀ obtainedꢀ asꢀ aꢀ
whiteꢀsolidꢀ(1.95ꢀg,ꢀ99%ꢀyield).ꢀ ꢀ
Poly‐3ꢀwasꢀobtainedꢀusingꢀtheꢀsameꢀsynthesisꢀmethodꢀbutꢀ
usingꢀ0.91ꢀgꢀofꢀethyleneꢀglycolꢀdimethacrylateꢀinsteadꢀofꢀ0.60ꢀgꢀ
DVB.ꢀ
2
.2.2.ꢀ ꢀ Synthesisꢀofꢀcompoundꢀ2,ꢀ(S)‐5,5’‐diBr‐BINAPOꢀ ꢀ
S)‐BINAPOꢀ (1.0ꢀ mmol,ꢀ 0.65ꢀ g)ꢀ wasꢀ dissolvedꢀ inꢀ dichloro‐
ethaneꢀ (DCE,ꢀ 15ꢀ mL),ꢀ followedꢀ byꢀ theꢀ additionꢀ ofꢀ FeBr ꢀ (2.2ꢀ
mmol,ꢀ0.65ꢀg)ꢀandꢀliquidꢀbromineꢀ(2.2ꢀmmol,ꢀ0.35ꢀg).ꢀAfterꢀre‐
fluxingꢀ forꢀ 12ꢀ h,ꢀ theꢀ solutionꢀ wasꢀ washedꢀ withꢀ 10%ꢀ NaHSO
aqueousꢀsolution,ꢀsaturatedꢀbrineꢀandꢀsaturatedꢀsodiumꢀbicar‐
bonateꢀaqueousꢀsolution,ꢀandꢀdriedꢀoverꢀNa SO .ꢀAfterꢀrefluxingꢀ
forꢀ12ꢀh,ꢀ(S)‐5,5’‐diBr‐BINAPOꢀwasꢀobtained.ꢀ
(
3
2.4.ꢀ ꢀ Characterizationꢀ
3
ꢀ
Nitrogenꢀ isothermsꢀ atꢀ –196ꢀ °Cꢀ wereꢀ measuredꢀ usingꢀ
QuantachromeꢀAutosorb‐1.ꢀTheꢀsamplesꢀwereꢀoutgassedꢀatꢀ120ꢀ
°Cꢀforꢀ10ꢀh.ꢀTheꢀporeꢀsizeꢀdistributionsꢀwereꢀcalculatedꢀusingꢀ
densityꢀfunctionalꢀtheoryꢀ(DFT)ꢀmethod.ꢀ ꢀ
2
4
Thermogravimetricꢀ analysisꢀ (TGA)ꢀ wasꢀ measuredꢀ usingꢀ
NETZSCHꢀSTAꢀ449F3,ꢀandꢀtheꢀsamplesꢀwereꢀheatedꢀfromꢀ40ꢀtoꢀ
1000ꢀ°Cꢀatꢀaꢀrateꢀofꢀ10ꢀ°C/minꢀunderꢀair.ꢀ ꢀ
Transmissionꢀelectronꢀmicroscopyꢀ(TEM)ꢀimagesꢀwereꢀtak‐
enꢀonꢀaꢀJEM‐2100ꢀwithꢀanꢀacceleratingꢀvoltageꢀofꢀ200ꢀkV.ꢀTheꢀ
morphologiesꢀ ofꢀ theꢀ polymersꢀ wereꢀ investigatedꢀ onꢀ aꢀ
JSM‐7800Fꢀscanningꢀelectronꢀmicroscopeꢀ(SEM).ꢀ ꢀ
Solid‐stateꢀNMRꢀspectraꢀwereꢀobtainedꢀonꢀaꢀVARIANꢀinfinityꢀ
plusꢀ 400ꢀ spectrometer.ꢀ Theꢀ 31Pꢀ MASꢀ NMRꢀ spectraꢀ wereꢀ rec‐
ordedꢀwithꢀaꢀ2.5ꢀmmꢀprobeꢀatꢀaꢀfrequencyꢀofꢀ161.8ꢀMHzꢀunderꢀ
aꢀmagicꢀangleꢀspinningꢀrateꢀofꢀ10ꢀkHzꢀandꢀaꢀdelayꢀofꢀ3ꢀs.ꢀTheꢀ
2
.2.3.ꢀ ꢀ Synthesisꢀofꢀcompoundꢀ3,ꢀ(S)‐5,5’‐divinyl‐BINAPOꢀ
S)‐5,5’‐diBr‐BINAPOꢀ(1.0ꢀmmol,ꢀ0.82ꢀg),ꢀpotassiumꢀvinyltri‐
fluoroborateꢀ (2.4ꢀ mmol,ꢀ 0.32ꢀ g)ꢀ andꢀ PdCl (dppf)CH Cl ꢀ (0.08ꢀ
(
2
2
2
mmol,ꢀ0.058ꢀg)ꢀwereꢀplacedꢀinꢀaꢀthree‐neckedꢀflask.ꢀn‐PrOHꢀ(10ꢀ
mL)ꢀ andꢀ triethylamineꢀ (2.0ꢀ mmol,ꢀ0.20ꢀ g)ꢀ wereꢀaddedꢀ toꢀ theꢀ
flask.ꢀTheꢀreactionꢀwasꢀmonitoredꢀbyꢀTLC.ꢀAfterꢀrefluxingꢀforꢀ3ꢀ
h,ꢀtheꢀsolventꢀwasꢀremovedꢀunderꢀvacuum.ꢀTheꢀprecipitateꢀwasꢀ
passedꢀthroughꢀaꢀsilicaꢀgelꢀcolumnꢀandꢀdriedꢀunderꢀvacuumꢀtoꢀ
giveꢀ (S)‐5,5’‐divinyl‐BINAPOꢀ asꢀ aꢀ whiteꢀ solidꢀ (0.565ꢀ g,ꢀ 80%ꢀ
yield).ꢀ
13
chemicalꢀshiftsꢀwereꢀreferencedꢀtoꢀ85%ꢀH
3
PO .ꢀ CꢀMASꢀNMRꢀ
4
2
.2.4.ꢀ ꢀ Synthesisꢀofꢀcompoundꢀ4,ꢀ(S)‐5,5’‐divinyl‐BINAPꢀ ꢀ
S)‐5,5’‐divinyl‐BINAPOꢀ (1.0ꢀ mmol,ꢀ 0.70ꢀ g),ꢀ trichlorosilaneꢀ
3.0ꢀmmol,ꢀ0.41ꢀg)ꢀandꢀphenylsilaneꢀ(3.0ꢀmmol,ꢀ0.32ꢀg)ꢀwereꢀ
spectraꢀwereꢀrecordedꢀunderꢀaꢀmagicꢀangleꢀspinningꢀrateꢀofꢀ6ꢀ
kHz.ꢀ ꢀ
(
(
TheꢀK‐edgeꢀX‐rayꢀabsorptionꢀfineꢀstructureꢀ(EXAFS)ꢀspectraꢀ
ofꢀRhꢀwereꢀobtainedꢀatꢀtheꢀBL14W1ꢀbeamlineꢀofꢀSSRF,ꢀSINAPꢀ
(Shanghai,ꢀ China)ꢀ withꢀ theꢀ useꢀ ofꢀ aꢀ Si(311)ꢀ crystalꢀ mono‐
chromator.ꢀTheꢀstorageꢀringꢀwasꢀoperatedꢀatꢀ3.5ꢀGeVꢀwithꢀin‐
jectionꢀcurrentsꢀofꢀ200ꢀmA.ꢀTheꢀdataꢀofꢀtheꢀsamplesꢀwereꢀrec‐
ordedꢀinꢀfluorescenceꢀmode.ꢀTheꢀXAFSꢀdataꢀwereꢀanalyzedꢀbyꢀ
usingꢀtheꢀDemeterꢀsoftwareꢀpackage.ꢀFourierꢀtransformationꢀofꢀ
placedꢀinꢀaꢀthree‐neckedꢀflaskꢀcontainingꢀtolueneꢀ(10ꢀmL).ꢀTheꢀ
reactionꢀwasꢀmonitoredꢀbyꢀTLC.ꢀAfterꢀrefluxingꢀforꢀ3ꢀh,ꢀtheꢀsol‐
ventꢀ wasꢀ cooledꢀ toꢀ 0ꢀ °Cꢀ followedꢀ byꢀ slowꢀ additionꢀ ofꢀ NaOHꢀ
aqueousꢀsolution.ꢀThenꢀtheꢀsolutionꢀwasꢀextractedꢀwithꢀwater,ꢀ
andꢀdriedꢀoverꢀNa
um.ꢀTheꢀprecipitateꢀwasꢀpassedꢀthroughꢀaꢀsilicaꢀgelꢀcolumnꢀandꢀ
2
SO .ꢀTheꢀsolventꢀwasꢀremovedꢀunderꢀvacu‐
4
3
driedꢀunderꢀvacuumꢀtoꢀgiveꢀ(S)‐5,5’‐divinyl‐BINAPꢀasꢀaꢀwhiteꢀ
solidꢀ(0.15ꢀg,ꢀ21%ꢀyield).ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl
theꢀEXAFSꢀdataꢀwasꢀappliedꢀtoꢀtheꢀk ‐weightedꢀfunctions.ꢀTheꢀ
1
3
)ꢀδꢀ5.47ꢀ(dd,ꢀ
theoreticalꢀscatteringꢀamplitudeꢀandꢀphase‐shiftꢀfunctionsꢀofꢀallꢀ

694ꢀ
TaoꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ38ꢀ(2017)ꢀ691–698ꢀ
theꢀpathsꢀforꢀfittingꢀtheꢀEXAFSꢀdataꢀwereꢀcalculatedꢀbyꢀFEFF6ꢀ
code.ꢀ
MPaꢀandꢀstirredꢀatꢀ80ꢀ°Cꢀforꢀ12ꢀh.ꢀTheꢀreactionꢀsolutionꢀwasꢀ
collectedꢀandꢀpassedꢀthroughꢀaꢀsilica‐gelꢀcolumnꢀwithꢀpetrole‐
umꢀ ether/ethylꢀ acetateꢀ (5:1ꢀv/v).ꢀTheꢀracemicꢀproductꢀofꢀtheꢀ
branchedꢀ aldehydeꢀ wasꢀ confirmedꢀ byꢀ GC‐MSꢀ (Agilentꢀ
2.5.ꢀ ꢀ Catalyticꢀprocessꢀ
7890‐5975C).ꢀ Anꢀ aliquotꢀ ofꢀ pureꢀ racemicꢀ branchedꢀ aldehydeꢀ
2
.5.1.ꢀ ꢀ Typicalꢀprocedureꢀforꢀasymmetricꢀhydroformylationꢀ
Asꢀaꢀtypicalꢀrun,ꢀaꢀmixtureꢀofꢀPoly‐1ꢀ(19ꢀmg,ꢀ0.0096ꢀmmolꢀP)ꢀ
wasꢀfurtherꢀtreatedꢀwithꢀJonesꢀreagentꢀtoꢀoxidizeꢀtheꢀaldehydesꢀ
toꢀcarboxylicꢀacids,ꢀwhichꢀwereꢀusedꢀtoꢀdetermineꢀtheirꢀreten‐
tionꢀtimes.ꢀ
andꢀRh(CO)
wasꢀheatedꢀtoꢀ100ꢀ°Cꢀforꢀ10ꢀhꢀunderꢀAr,ꢀthenꢀstyreneꢀwasꢀadd‐
ed.ꢀAfterꢀpurgingꢀwithꢀsyngasꢀ(H /COꢀ=ꢀ1:1)ꢀ4ꢀtimes,ꢀtheꢀpres‐
2
(acae)ꢀ(0.25ꢀmg,ꢀ0.00096ꢀmmol)ꢀinꢀtolueneꢀ(2ꢀmL)ꢀ
2
3.ꢀ ꢀ Resultsꢀandꢀdiscussionꢀ
3.1.ꢀ ꢀ Characterizationꢀresultsꢀ
sureꢀwasꢀadjustedꢀtoꢀtheꢀdesiredꢀvalueꢀandꢀtheꢀreactionꢀmixtureꢀ
wasꢀstirredꢀatꢀ80ꢀ°Cꢀforꢀ24ꢀh.ꢀAfterꢀtheꢀreaction,ꢀtheꢀcatalystꢀwasꢀ
separatedꢀ byꢀ centrifugation,ꢀ andꢀ theꢀ productꢀ (yieldꢀ forꢀ alde‐
hydesꢀ andꢀ regioselectivityꢀ forꢀ 2‐phenylpropionaldehyde)ꢀ wasꢀ
analyzedꢀbyꢀgasꢀchromatographyꢀ(Agilentꢀ7890Bꢀgasꢀchroma‐
tographyꢀequippedꢀwithꢀaꢀflameꢀionizationꢀdetectorꢀandꢀaꢀCy‐
clodex‐Bꢀ capillaryꢀ column).ꢀ Aꢀ sampleꢀ ofꢀ theꢀ reactionꢀ mixtureꢀ
wasꢀ treatedꢀ withꢀ Jonesꢀ reagentꢀ toꢀ oxidizeꢀ theꢀ aldehydesꢀ toꢀ
carboxylicꢀ acids,ꢀ whichꢀ wereꢀ usedꢀ toꢀ determineꢀ theꢀ enantio‐
mericꢀexcessꢀ(ee)ꢀbyꢀGC.ꢀ
13Cꢀmagicꢀangleꢀspinningꢀ(MAS)ꢀNMRꢀspectraꢀwereꢀusedꢀtoꢀ
characterizeꢀtheꢀpolymersꢀ(Fig.ꢀ1(a)).ꢀAllꢀtheꢀpolymersꢀshowedꢀ
broadꢀresonanceꢀpeaksꢀfromꢀ120ꢀtoꢀ150ꢀppm,ꢀwhichꢀwereꢀas‐
signedꢀtoꢀtheꢀaromaticꢀcarbons.ꢀTheꢀsignalsꢀfromꢀ20ꢀtoꢀ55ꢀppmꢀ
wereꢀ attributedꢀ toꢀ theꢀ methyleneꢀ linker.ꢀ Theꢀ structureꢀ infor‐
mationꢀofꢀRh/Poly‐1ꢀremainsꢀtheꢀsameꢀasꢀthatꢀofꢀPoly‐1ꢀinꢀtheꢀ
13Cꢀ MASꢀ NMR.ꢀ Theꢀ positionꢀ ofꢀ theꢀ spinningꢀ sidebandsꢀ inꢀ
Rh/Poly‐1ꢀwasꢀdifferentꢀfromꢀthatꢀofꢀPoly‐1.ꢀThisꢀisꢀbecauseꢀtheꢀ
13CꢀMASꢀNMRꢀspectraꢀofꢀRh/Poly‐1ꢀwasꢀrecordedꢀunderꢀaꢀmag‐
icꢀ angleꢀ spinningꢀ rateꢀ ofꢀ 9ꢀ kHz,ꢀ whereasꢀ theꢀ otherꢀ materialsꢀ
wereꢀrecordedꢀunderꢀaꢀmagicꢀangleꢀspinningꢀrateꢀofꢀ6ꢀkHz.ꢀAd‐
ditionally,ꢀ theꢀ 31Pꢀ MASꢀ NMRꢀ spectrumꢀ ofꢀ Poly‐1ꢀ showedꢀ oneꢀ
mainꢀ signalꢀ atꢀ –14.5ꢀ ppmꢀ (Fig.ꢀ 1(b)),ꢀ whichꢀ wasꢀ atꢀ theꢀ sameꢀ
2
.5.2.ꢀ ꢀ Typicalꢀprocedureꢀforꢀpreparingꢀracemicꢀproductsꢀ
PPh
ꢀ (30.0ꢀ mg,ꢀ 0.114ꢀ mmolꢀ P),ꢀ Rh(CO) (acae)ꢀ (3.0ꢀ mg,ꢀ
.0114ꢀmmol),ꢀ4‐chlorostyreneꢀ(1.5ꢀg,ꢀ9.71ꢀmmol)ꢀandꢀtolueneꢀ
3
2
0
(2ꢀmL)ꢀwereꢀmixedꢀinꢀaꢀ25‐mLꢀautoclave.ꢀAfterꢀpurgingꢀwithꢀ
syngasꢀ(H /COꢀ=ꢀ1:1)ꢀ4ꢀtimes,ꢀtheꢀpressureꢀwasꢀadjustedꢀtoꢀ3.0ꢀ
2
(a)
*
*
(b)
*
*
(1)
(1)
(2)
*
(3)
*
*
*
*
(4)
(4)
250
200
150
100
50
0
-50
100 80 60 40 20
0
-20 -40 -60
Chemical shift (ppm)
Chemical shift (ppm)
0.24
0.22
0.20
0.18
0.16
0.14
0.12
0.10
0.08
1
400 (c)
(1)
(d)
1
1
200
(2)
000
(
1)
8
6
4
2
00
00
00
00
0
(3)
(4)
(
2)
0.0
0.2
0.4
0.6
0.8
1.0
1
10
Relative pressure (P/P
0
)
Pore width (nm)
13
31
Fig.ꢀ1.ꢀ(a)ꢀ CꢀCP/MASꢀNMR,ꢀ(b)ꢀ PꢀMASꢀNMR,ꢀ(c)ꢀN
2
ꢀisothermsꢀandꢀ(d)ꢀporeꢀsizeꢀdistributionꢀofꢀ(1)ꢀPoly‐1,ꢀ(2)ꢀPoly‐2,ꢀ(3)ꢀPoly‐3ꢀandꢀ(4)ꢀRh/Poly‐1.ꢀ
Asterisksꢀdenoteꢀspinningꢀsidebands.ꢀ

ꢀ
TaoꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ38ꢀ(2017)ꢀ691–698ꢀ
695ꢀ
positionꢀ asꢀ theꢀ ligand.ꢀ Theseꢀ observationsꢀ indicatedꢀ thatꢀ theꢀ
BINAPꢀmoietiesꢀwereꢀstableꢀduringꢀtheꢀsolvothermalꢀpolymer‐
Tableꢀ2ꢀ
Theꢀ optimizationꢀ ofꢀ parametersꢀ forꢀ hydroformylationꢀ reactionꢀ byꢀ
Rh/Poly‐1.ꢀ
31
izationꢀprocess.ꢀAfterꢀloadingꢀtheꢀRhꢀspecies,ꢀtheꢀ PꢀMASꢀNMRꢀ
spectrumꢀ ofꢀ Rh/Poly‐1ꢀ exhibitedꢀ aꢀ relativelyꢀ highꢀ resonanceꢀ
signalꢀatꢀ25.1ꢀppmꢀowingꢀtoꢀphosphorousꢀoxide.ꢀAꢀresonanceꢀ
peakꢀatꢀ52.0ꢀppmꢀwasꢀalsoꢀpresent,ꢀwhichꢀwasꢀassignedꢀtoꢀtheꢀ
unprotectedꢀphosphineꢀcoordinatedꢀwithꢀtheꢀRhꢀspeciesꢀ[34].ꢀ ꢀ
a
a
Entryꢀ
1ꢀ ꢀ
Temp.ꢀ(°C) Pꢀ(MPa)ꢀ Yieldꢀ
ꢀ(%)ꢀ
i/nꢀ
14.8
12.4
11.3
10.0
ꢀ 9.1ꢀ
ꢀ 6.3ꢀ
ꢀ 8.5ꢀ
11.2
11.8
12.0
12.3
eeꢀ ꢀ(%)ꢀ
ꢀ 60ꢀ
ꢀ 70ꢀ
ꢀ 80ꢀ
ꢀ 90ꢀ
100ꢀ
110ꢀ
ꢀ 80ꢀ
ꢀ 80ꢀ
ꢀ 80ꢀ
ꢀ 80ꢀ
ꢀ 80ꢀ
1ꢀ
1ꢀ
1ꢀ
1ꢀ
1ꢀ
ꢀ 7.6ꢀ
23.1ꢀ
56.7ꢀ
74.1ꢀ
96.9ꢀ
93.5ꢀ
93.5ꢀ
68.3ꢀ
34.4ꢀ
12.1ꢀ
ꢀ 7.1ꢀ
56.3ꢀ
30.6ꢀ
37.8ꢀ
28.3ꢀ
20.3ꢀ
25.3ꢀ
58.9ꢀ
42.0ꢀ
38.7ꢀ
35.4ꢀ
31.6ꢀ
2ꢀ ꢀ
3ꢀ ꢀ
4ꢀ ꢀ
5ꢀ ꢀ
Theꢀ poreꢀ propertiesꢀ ofꢀ theꢀ materialsꢀ wereꢀ analyzedꢀ byꢀ N ꢀ
2
physisorptionꢀ isothermsꢀ (Fig.ꢀ 1(c)).ꢀ Theꢀ curvesꢀ ofꢀ Poly‐1ꢀ andꢀ
Poly‐2ꢀcollectedꢀatꢀ–196ꢀ°Cꢀexhibitedꢀcombinedꢀfeaturesꢀofꢀtypeꢀ
6ꢀ ꢀ
7ꢀ
1ꢀ
ꢀ 0.2ꢀ
ꢀ 0.5ꢀ
ꢀ 1.5ꢀ
3ꢀ
8
ꢀ
IꢀandꢀtypeꢀIVꢀhysteresisꢀwithꢀanꢀobviouslyꢀsteepꢀstepꢀinꢀtheꢀP/P
ꢀ 0.01ꢀ regionꢀ andꢀ hysteresisꢀ loopsꢀ inꢀ theꢀ 0.60ꢀ <ꢀ P/P ꢀ <ꢀ 0.95ꢀ
region,ꢀ whichꢀ suggestsꢀ thatꢀ micro‐ꢀ andꢀ mesoporesꢀ wereꢀ pre‐
0
ꢀ
9
ꢀ
<
0
1
1
0ꢀ
1ꢀ
4ꢀ
sentꢀ inꢀ theꢀ polymer.ꢀ Theseꢀ dataꢀ wereꢀ confirmedꢀ byꢀ theꢀ poreꢀ
sizeꢀ distributionꢀ curvesꢀ calculatedꢀ byꢀ nonlocalꢀ densityꢀ func‐
tionalꢀtheoryꢀmethodꢀ(NLDFT);ꢀtheꢀporeꢀsizesꢀofꢀtwoꢀtypesꢀofꢀ
poresꢀ wereꢀ distributedꢀ atꢀ approximatelyꢀ 0.5–1.5ꢀ andꢀ 2.5–10ꢀ
nm,ꢀ respectivelyꢀ (Fig.ꢀ 1(d)).ꢀ Theꢀ Brunauer‐Emmet‐Tellerꢀ sur‐
Reactionꢀconditions:ꢀ2ꢀmLꢀtoluene,ꢀH /COꢀ=ꢀ1:1,ꢀ0.00096ꢀmmolꢀRhꢀwithꢀ
2
theꢀmolarꢀratioꢀofꢀP/Rhꢀ=ꢀ10,ꢀS/Cꢀ=ꢀ2000,ꢀ24ꢀh.ꢀ ꢀ
aꢀ
DeterminedꢀbyꢀGCꢀonꢀaꢀCyclodex‐Bꢀcapillaryꢀcolumn.ꢀ
ꢀ
ties;ꢀ theꢀ highestꢀ enantioselectivityꢀ (37.8%)ꢀ wasꢀ affordedꢀ byꢀ
Rh/Poly‐1ꢀusingꢀtolueneꢀasꢀaꢀsolvent.ꢀTolueneꢀwasꢀselectedꢀasꢀaꢀ
solventꢀtoꢀinvestigateꢀtheꢀeffectꢀofꢀtemperatureꢀonꢀtheꢀreactionꢀ
inꢀ theꢀ rangeꢀ ofꢀ 60–110ꢀ °Cꢀ (Tableꢀ 2,ꢀ entriesꢀ 1–6).ꢀ Whenꢀ theꢀ
temperatureꢀ increased,ꢀ theꢀ yieldꢀ significantlyꢀ increasedꢀ fromꢀ
faceꢀareasꢀofꢀPoly‐1ꢀandꢀPoly‐2ꢀwereꢀestimatedꢀtoꢀbeꢀ697ꢀandꢀ
2
9
97ꢀm /g,ꢀrespectively,ꢀandꢀtheꢀporeꢀvolumesꢀwereꢀcalculatedꢀ
3
toꢀbeꢀ0.68ꢀandꢀ1.19ꢀcm /g,ꢀrespectively.ꢀRh/Poly‐1ꢀexhibitedꢀaꢀ
2
3
lowerꢀ surfaceꢀ areaꢀ andꢀ poreꢀ volumeꢀ (490ꢀ m /g,ꢀ 0.56ꢀ cm /g,ꢀ
respectively)ꢀ thanꢀ Poly‐1,ꢀ becauseꢀ thatꢀ partꢀ ofꢀ theꢀ materialꢀ
spaceꢀ wasꢀ occupiedꢀ afterꢀ loadingꢀ withꢀ Rhꢀ species.ꢀ Comparedꢀ
7.6%ꢀtoꢀ93.5%.ꢀInꢀsharpꢀcontrast,ꢀtheꢀregioselectivityꢀandꢀenan‐
tioselectivityꢀbothꢀdecreasedꢀwithꢀtheꢀincreaseꢀinꢀtheꢀtempera‐
ture.ꢀAsꢀaꢀresult,ꢀ80ꢀ°Cꢀwasꢀselectedꢀasꢀanꢀappropriateꢀtemper‐
atureꢀ forꢀ furtherꢀ investigation.ꢀ Theꢀ impactꢀ ofꢀ theꢀ pressureꢀ ofꢀ
withꢀ theꢀ co‐monomersꢀ divinylꢀ benzeneꢀ andꢀ 1,3,5‐tri(4‐vi‐
ꢀ
nylphenyl)benzene,ꢀwhichꢀareꢀrigidꢀbulkyꢀblocks,ꢀtheꢀethyleneꢀ
glycolꢀ dimethacrylateꢀ hasꢀ longerꢀ carbonꢀ chainsꢀ withꢀ aꢀ linearꢀ
structureꢀandꢀaffordedꢀaꢀnonporousꢀPoly‐3.ꢀAnotherꢀreasonꢀtoꢀ
explainꢀ theꢀ condensedꢀ structureꢀ ofꢀ Poly‐3ꢀ isꢀ theꢀ hydrogenꢀ
bondingꢀbetweenꢀtheꢀhydrogenꢀatomsꢀandꢀtheꢀcarboxylꢀgroups.ꢀ
H
/COꢀwasꢀinvestigatedꢀ(Tableꢀ2,ꢀentriesꢀ7–11).ꢀWhenꢀtheꢀreac‐
2
tionꢀpressureꢀwasꢀdecreasedꢀfromꢀ4.0ꢀtoꢀ0.2ꢀMPa,ꢀtheꢀyieldꢀin‐
creasedꢀfromꢀ7.1%ꢀtoꢀ93.5%,ꢀalthoughꢀtheꢀregioselectivityꢀde‐
creasedꢀfromꢀ12.3%ꢀtoꢀ8.5%.ꢀAnꢀunexpectedlyꢀhighꢀenantiose‐
lectivityꢀ (58.9%)ꢀ wasꢀ achievedꢀ whenꢀ theꢀ reactionꢀ wasꢀ per‐
formedꢀnearꢀatmosphericꢀpressureꢀ(0.2ꢀMPa).ꢀ
3.2.ꢀ ꢀ Catalyticꢀactivityꢀ
Theꢀcatalyticꢀperformanceꢀofꢀtheꢀthreeꢀcatalystsꢀ(Rh/Poly‐1,ꢀ
Rh/Poly‐2ꢀandꢀRh/Poly‐3)ꢀwasꢀexaminedꢀunderꢀaꢀpressureꢀofꢀ
TheꢀRh‐basedꢀcatalystsꢀwereꢀaffordedꢀbyꢀimpregnatingꢀtheꢀ
polymersꢀwithꢀRh(CO) (acac)ꢀdissolvedꢀinꢀtoluene.ꢀStyreneꢀwasꢀ
2
0.2ꢀMPaꢀatꢀ80ꢀ°Cꢀforꢀ24ꢀhꢀ(Tableꢀ3,ꢀentriesꢀ1–3).ꢀTheseꢀcatalystsꢀ
chosenꢀasꢀaꢀsubstrateꢀtoꢀdetectꢀtheꢀasymmetricꢀhydroformyla‐
tionꢀactivitiesꢀofꢀtheꢀpolymericꢀcatalysts.ꢀAlthoughꢀtheꢀcatalystsꢀ
wereꢀinsoluble,ꢀtheyꢀwereꢀproneꢀtoꢀswellingꢀinꢀmanyꢀsolvents.ꢀ
Therefore,ꢀweꢀinitiallyꢀchoseꢀthreeꢀsolventsꢀthatꢀhaveꢀbeenꢀusedꢀ
mostꢀ frequentlyꢀ inꢀ asymmetricꢀ hydroformylationꢀ toꢀ testꢀ theꢀ
catalyticꢀ performanceꢀ ofꢀ Rh/Poly‐1ꢀ (Tableꢀ 1).ꢀ Theꢀ resultsꢀ
showedꢀthatꢀtheꢀthreeꢀsolventsꢀgaveꢀsimilarꢀyieldꢀforꢀaldehydes,ꢀ
butꢀ providedꢀ differentꢀ regioselectivitiesꢀ andꢀ enantioselectivi‐
exhibitedꢀ similarꢀ yieldsꢀ (92%–94%),ꢀ whereasꢀ Rh/Poly‐1ꢀ
showedꢀtheꢀbestꢀregioselectivityꢀ(8.5%)ꢀandꢀenantioselectivityꢀ
(58.9%).ꢀTheꢀresultsꢀshowedꢀthatꢀtheꢀporeꢀstructuresꢀhadꢀlittleꢀ
effectꢀonꢀtheꢀyields,ꢀbutꢀhadꢀaꢀclearꢀeffectꢀonꢀtheꢀregioselectivityꢀ
andꢀ enantioselectivity.ꢀ Inꢀ theꢀ swollenꢀ state,ꢀ theꢀ backbonesꢀ ofꢀ
theꢀpolymer‐supportedꢀcatalystsꢀwereꢀflexibleꢀandꢀfreelyꢀmov‐
Tableꢀ3ꢀ
Asymmetricꢀhydroformylationꢀofꢀstyreneꢀbyꢀdifferentꢀcatalysts.ꢀ
Tableꢀ1ꢀ
Theꢀ performanceꢀ ofꢀ Rh/Poly‐1ꢀ forꢀ hydroformylationꢀ inꢀ variousꢀ sol‐
vents.ꢀ
ꢀ
a
a
Entryꢀ
Catalystꢀ
Rh/Ploy‐1ꢀ
Rh/Ploy‐2ꢀ
Rh/Ploy‐3ꢀ
Rꢀ
Hꢀ
Hꢀ
Hꢀ
Hꢀ
Clꢀ
Brꢀ
OCH
Yieldꢀ ꢀ(%)ꢀ i/nꢀ
eeꢀ ꢀ(%)
1
2
3
4
5
6
ꢀ ꢀ
ꢀ ꢀ
ꢀ ꢀ
ꢀ
ꢀ
ꢀ
93.5ꢀ
94.6ꢀ
92.2ꢀ
94.9ꢀ
98.4ꢀ
88.4ꢀ
58.5ꢀ
ꢀ 8.5ꢀ
ꢀ 8.0ꢀ
ꢀ 6.8ꢀ
ꢀ 8.1ꢀ
11.9ꢀ
12.6ꢀ
ꢀ 8.1ꢀ
58.9ꢀ
45.1ꢀ
30.7ꢀ
35.3ꢀ
21.3ꢀ
36.0ꢀ
50.7ꢀ
ꢀ
a
i/nꢀbꢀ
11.7ꢀ
11.3ꢀ
5.12ꢀ
a
Solventꢀ
Benzeneꢀ
Tolueneꢀ
THFꢀ
Yieldꢀ ꢀ(%)ꢀ
eeꢀ ꢀ(%)ꢀ
28.9ꢀ
37.8ꢀ
17.5ꢀ
45.5ꢀ
56.7ꢀ
52.5ꢀ
Rh‐BINAP
ꢀ
bꢀ
Rh/Ploy‐1ꢀ
Rh/Ploy‐1ꢀ
Rh/Ploy‐1ꢀ
2
Reactionꢀ conditions:ꢀ 2ꢀ mLꢀ solvents,ꢀ H /COꢀ =ꢀ 1:1ꢀ (1ꢀ MPa),ꢀ 0.00096ꢀ
7ꢀ
3
ꢀ
mmolꢀRhꢀwithꢀtheꢀmolarꢀratioꢀofꢀP/Rhꢀ=ꢀ10,ꢀS/Cꢀ=ꢀ2000,ꢀ80ꢀ°C,ꢀ24ꢀh.ꢀ ꢀ
Reactionꢀ conditions:ꢀ 2ꢀ mLꢀ toluene,ꢀ H /COꢀ =ꢀ 1:1ꢀ (0.2ꢀ MPa),ꢀ 0.00096ꢀ
2
aꢀ
DeterminedꢀbyꢀGCꢀonꢀaꢀCyclodex‐Bꢀcapillaryꢀcolumn.ꢀ ꢀ
mmolꢀRhꢀwithꢀtheꢀmolarꢀratioꢀofꢀP/Rhꢀ=ꢀ10,ꢀS/Cꢀ=ꢀ2000,ꢀ24ꢀh.ꢀ ꢀ
bꢀ
aꢀ
Molarꢀratioꢀofꢀbranchedꢀtoꢀlinearꢀaldehydeꢀinꢀtheꢀproducts,ꢀdeterminedꢀ
DeterminedꢀbyꢀGCꢀonꢀaꢀCyclodex‐Bꢀcapillaryꢀcolumn.ꢀ ꢀ
HomogeneousꢀcatalystꢀofꢀRh‐BINAPꢀsystemꢀwithꢀP/Rhꢀ=ꢀ10.ꢀ
bꢀ
byꢀGC.ꢀ

696ꢀ
TaoꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ38ꢀ(2017)ꢀ691–698ꢀ
able.ꢀTherefore,ꢀtheꢀsubstrateꢀcouldꢀobtainꢀrapidꢀaccessꢀtoꢀtheꢀ
activeꢀsitesꢀofꢀtheꢀheterogeneousꢀcatalysts.ꢀMeanwhile,ꢀtheꢀrigidꢀ
andꢀbulkyꢀ blocksꢀaroundꢀtheꢀ BINAP,ꢀsuchꢀ asꢀdivinylꢀ benzeneꢀ
andꢀ 1,3,5‐tri(4‐vinylphenyl)benzene,ꢀ fabricatedꢀ irregularꢀ andꢀ
stericꢀ poreꢀ structures,ꢀ whichꢀ couldꢀ beꢀ favorableꢀ forꢀ theꢀ for‐
mationꢀ ofꢀ chiralꢀ pockets.ꢀ Efficientꢀ asymmetricꢀ hydroformyla‐
tionsꢀwereꢀconductedꢀwhenꢀtheꢀsubstrateꢀwasꢀcoordinatedꢀwithꢀ
Rhꢀspeciesꢀinꢀtheꢀchiralꢀpockets,ꢀandꢀasꢀanticipated,ꢀhighꢀenan‐
tioselectivitiesꢀ wereꢀ obtained.ꢀ Theꢀ Rh/Poly‐1ꢀ andꢀ Rh/Poly‐2ꢀ
catalystsꢀbothꢀexhibitedꢀhigherꢀenantioselectivityꢀthanꢀtheꢀho‐
mogeneousꢀsystem.ꢀHowever,ꢀRh/Poly‐3,ꢀwhichꢀcontainedꢀlongꢀ
carbonꢀ chainꢀ linksꢀ (ethyleneꢀ glycolꢀ dimethacrylate)ꢀ andꢀ
showedꢀ propertiesꢀ ofꢀ aꢀ nonporousꢀ bulkꢀ materialꢀ (noꢀ chiralꢀ
pocketꢀexisted),ꢀonlyꢀexhibitedꢀanꢀenantioselectivityꢀofꢀ30.7%ꢀ
andꢀaꢀlowꢀregioselectivityꢀofꢀ6.8%.ꢀRh/Poly‐1ꢀwasꢀalsoꢀusedꢀtoꢀ
catalyzeꢀ 4‐substitutedꢀ styreneꢀ derivativesꢀ (Tableꢀ 3,ꢀ entriesꢀ
Experiment
Fitting
(
1)
(
2)
0
1
2
3
4
5
6
R (Å)
3
Fig.ꢀ 3.ꢀ Theꢀ Rhꢀ K‐edgeꢀ k ‐weightedꢀ Fourierꢀ transformꢀ spectraꢀ fromꢀ
EXAFS.ꢀ(1)ꢀFreshꢀRh/Poly‐1;ꢀ(2)ꢀUsedꢀRh/Poly‐1.ꢀ
5
–7).ꢀ Theꢀ presenceꢀ ofꢀ substratesꢀ containingꢀ electron‐
with‐
ꢀ
drawingꢀgroups,ꢀsuchꢀasꢀClꢀandꢀBr,ꢀseemedꢀtoꢀdecreaseꢀtheꢀeeꢀ
values,ꢀ althoughꢀ theyꢀ gaveꢀ goodꢀ conversionꢀ results.ꢀ Theꢀ
Rh/Poly‐1ꢀgaveꢀaꢀhighꢀeeꢀvalueꢀofꢀ50.7%ꢀwhenꢀ4‐
ꢀ
methoxysty‐
reneꢀwasꢀusedꢀasꢀaꢀsubstrate.ꢀ
Consideringꢀ theꢀ catalystꢀ stabilityꢀ andꢀ reusabilityꢀ wereꢀ ofꢀ
primaryꢀ interestsꢀ inꢀ heterogeneousꢀ catalysis,ꢀ weꢀ investigatedꢀ
theꢀpossibilityꢀofꢀrecyclingꢀRh/Poly‐1ꢀ(Fig.ꢀ2).ꢀWhenꢀtheꢀreac‐
tionꢀwasꢀfinished,ꢀtheꢀcatalystꢀwasꢀseparatedꢀbyꢀcentrifugation,ꢀ
washedꢀwithꢀtolueneꢀ(performedꢀunderꢀnitrogenꢀatmosphere)ꢀ
andꢀthenꢀtheꢀcatalystꢀwasꢀusedꢀdirectlyꢀforꢀtheꢀnextꢀroundꢀreac‐
tion.ꢀ Theꢀ catalystꢀ wasꢀ reusedꢀ sevenꢀ timesꢀ withoutꢀ significantꢀ
lossꢀ ofꢀ activityꢀ andꢀ enantioselectivity.ꢀ Theꢀ fluctuationꢀ ofꢀ theꢀ
productꢀyieldꢀandꢀeeꢀvaluesꢀwasꢀascribedꢀtoꢀtheꢀreactionꢀpres‐
Fig.ꢀ 4.ꢀ High‐angleꢀ annularꢀ dark‐fieldꢀ scanningꢀ transmissionꢀ electronꢀ
microscopyꢀ(HAADF‐STEM)ꢀimagesꢀofꢀtheꢀfreshꢀRh/Poly‐1ꢀ(a)ꢀandꢀusedꢀ
Rh/Poly‐1ꢀ(b).ꢀ
ToꢀconfirmꢀtheꢀcoordinationꢀstatusꢀofꢀtheꢀRhꢀspeciesꢀinꢀourꢀ
heterogeneousꢀ catalyst,ꢀ extendedꢀX‐rayꢀabsorptionꢀfineꢀstruc‐
tureꢀ spectroscopyꢀ (EXAFS)ꢀ andꢀ high‐angleꢀ annularꢀ dark‐fieldꢀ
scanningꢀ transmissionꢀ electronꢀ microscopyꢀ (HAADF‐STEM)ꢀ
characterizationꢀ wereꢀ employedꢀ forꢀ theꢀ freshꢀ andꢀ usedꢀ
Rh/Poly‐1ꢀ(Figs.ꢀ3ꢀandꢀ4).ꢀAccordingꢀtoꢀtheꢀcurve‐fittingꢀresults,ꢀ
inꢀtheꢀfreshꢀRh/Poly‐1ꢀeachꢀRhꢀatomꢀisꢀcoordinatedꢀwithꢀthreeꢀ
Pꢀatomsꢀ(derivedꢀformꢀBINAP)ꢀandꢀtwoꢀOꢀatomsꢀ(derivedꢀfromꢀ
sureꢀofꢀH
/CO.ꢀWeꢀpreviouslyꢀshowedꢀthatꢀtheꢀreactionꢀpres‐
2
sureꢀhadꢀaꢀsignificantꢀinfluenceꢀonꢀtheꢀactivityꢀandꢀenantiose‐
lectivity.ꢀMeanwhile,ꢀtheꢀyieldꢀofꢀtheꢀproductꢀwasꢀinꢀtheꢀlevelꢀofꢀ
middleꢀwhenꢀtheꢀreactionꢀtimeꢀofꢀtheꢀrecyclingꢀtestꢀwasꢀ10ꢀh.ꢀ
Theꢀinitialꢀreactionꢀpressureꢀwasꢀonlyꢀ0.2ꢀMPa;ꢀtherefore,ꢀsmallꢀ
changesꢀinꢀtheꢀpressureꢀduringꢀtheꢀreactionꢀwouldꢀhaveꢀaꢀcer‐
tainꢀimpactꢀonꢀtheꢀreactionꢀresults.ꢀTheꢀexcellentꢀstabilityꢀofꢀtheꢀ
catalystꢀ couldꢀ beꢀ ascribedꢀ toꢀ theꢀ covalentlyꢀ linkedꢀ methyleneꢀ
groups,ꢀwhichꢀfirmlyꢀtiedꢀtheꢀchiralꢀBINAPꢀligand.ꢀ
acetylacetoneꢀinꢀtheꢀRh(CO)
(acac)ꢀprecursor)ꢀ(Tableꢀ4).ꢀMoreꢀ
2
importantly,ꢀnoꢀRh‒Rhꢀbondꢀcanꢀbeꢀdetectedꢀinꢀtheꢀfreshꢀsam‐
pleꢀofꢀRh/Poly‐1,ꢀwhichꢀindicatedꢀthatꢀtheꢀRhꢀspeciesꢀwereꢀco‐
ordinatedꢀwithꢀchiralꢀligandsꢀandꢀefficientꢀmolecularꢀcatalystsꢀ
wereꢀ afforded.ꢀ Thisꢀ wasꢀ furtherꢀ confirmedꢀ byꢀ theꢀ HAADF‐
ꢀ
7
6
5
4
3
2
1
0
0
0
0
0
0
0
0
STEMꢀ imageꢀ (Fig.ꢀ 4).ꢀ Afterꢀ Rh/Poly‐1ꢀ wasꢀ usedꢀ sevenꢀ times,ꢀ
oneꢀRhꢀatomꢀwasꢀcoordinatedꢀwithꢀthreeꢀPꢀatoms,ꢀoneꢀCOꢀmol‐
eculeꢀ (Tableꢀ 4)ꢀ andꢀ oneꢀ Hꢀ atom.ꢀ Thisꢀ resultꢀ isꢀ inꢀ accordanceꢀ
withꢀtheꢀmechanismꢀofꢀRh‐basedꢀhomogeneousꢀhydroformyla‐
tionꢀcatalysis,ꢀinꢀwhichꢀtheꢀacetylꢀacetoneꢀmoleculeꢀisꢀreplacedꢀ
byꢀtheꢀCOꢀandꢀHꢀtoꢀformꢀtheꢀactiveꢀspeciesꢀforꢀhydroformyla‐
Yield
ee
i/n
Tableꢀ4ꢀ
Theꢀcurve‐fittingꢀanalysisꢀofꢀtheꢀEXAFSꢀtraces.ꢀ
2
3
Rh/Poly‐1ꢀ
Freshꢀ
ꢀ
Usedꢀ
ꢀ
Shellꢀ
Rh‒Pꢀ
Rh‒Oꢀ
Rh‒Pꢀ
Rh‒Cꢀ
Rh‒Rhꢀ
Nꢀ
Rꢀ(Å)ꢀ
2.13ꢀ
2.11ꢀ
2.13ꢀ
1.69ꢀ
2.83ꢀ
σ 10 ꢀ
3.0ꢀ
Rꢀfactorꢀ
0.013ꢀ
3.0ꢀ
2.0ꢀ
3.0ꢀ
1.0ꢀ
1.5ꢀ
3.0ꢀ
1.0ꢀ
4.9ꢀ
ꢀ
1
2
3
4
Run
5
6
7
0.007ꢀ
ꢀ
ꢀ
Fig.ꢀ2.ꢀRecyclingꢀstudiesꢀforꢀtheꢀasymmetricꢀhydroformylationꢀofꢀsty‐
reneꢀbyꢀRh/Poly‐1.ꢀReactionꢀconditions:ꢀ2ꢀmLꢀtoluene,ꢀH /COꢀ=ꢀ1:1ꢀ(0.2
MPa),ꢀ0.00096ꢀmmolꢀRhꢀwithꢀaꢀmolarꢀratioꢀofꢀP/Rhꢀ=ꢀ10,ꢀS/Cꢀ=ꢀ2000,ꢀ10
h.ꢀ
ꢀ
3.0ꢀ
2
N,ꢀcoordinationꢀnumber;ꢀR,ꢀdistanceꢀbetweenꢀabsorberꢀandꢀbackscatter;ꢀ
2
σ ,ꢀDebye‐Wallerꢀfactor.ꢀ

ꢀ
TaoꢀWangꢀetꢀal.ꢀ/ꢀChineseꢀJournalꢀofꢀCatalysisꢀ38ꢀ(2017)ꢀ691–698ꢀ
697ꢀ
tionꢀ [7,8].ꢀ Theseꢀ observationsꢀ indicatedꢀ thatꢀ justꢀ likeꢀ theꢀ ho‐
mogeneousꢀcatalysisꢀmechanism,ꢀitꢀwasꢀreasonableꢀtoꢀattributeꢀ
theꢀimprovementꢀofꢀenantioselectivityꢀinꢀtheꢀcaseꢀofꢀRh/Poly‐1ꢀ
catalystꢀtoꢀaꢀfavorableꢀchiralꢀpocketꢀeffect.ꢀInꢀaddition,ꢀonlyꢀaꢀ
fewꢀRh‒Rhꢀbondsꢀwereꢀdetectedꢀafterꢀtheꢀseventhꢀrunꢀ(Tableꢀ
[6] N.ꢀSakai,ꢀS.ꢀ Mano,ꢀK.ꢀNozaki,ꢀ H.ꢀTakaya,ꢀ J.ꢀAm.ꢀChem.ꢀSoc.,ꢀ1993,ꢀ
115,ꢀ7033–7034.ꢀ
[
[
[
7] I.ꢀdelꢀRio,ꢀW.ꢀG.ꢀJ.ꢀdeꢀLange,ꢀP.ꢀW.ꢀN.ꢀM.ꢀvanꢀLeeuwen,ꢀC.ꢀClaver,ꢀJ.ꢀ
Chem.ꢀSoc.,ꢀDaltonꢀTrans.,ꢀ2001,ꢀ1293–1300.ꢀ
8] M.ꢀ Dieguez,ꢀ M.ꢀ M.ꢀ Pereira,ꢀ A.ꢀ M.ꢀ Masdeu‐Bulto,ꢀ C.ꢀ Claver,ꢀ J.ꢀ C.ꢀ
Bayon,ꢀJ.ꢀMol.ꢀCatal.ꢀA,ꢀ1999,ꢀ143,ꢀ111–122.ꢀ
9] A.ꢀM.ꢀMasdeu‐Bulto,ꢀA.ꢀOrejon,ꢀA.ꢀCastellanos,ꢀS.ꢀCastillon,ꢀC.ꢀClaver,ꢀ
Tetrahedron:ꢀAsymmetry,ꢀ1996,ꢀ7,ꢀ1829–1834.ꢀ
4).ꢀTheꢀcontentꢀofꢀRhꢀparticlesꢀwasꢀveryꢀlowꢀaccordingꢀtoꢀtheꢀ
HAADF‐STEMꢀimage,ꢀandꢀtheꢀRhꢀparticlesꢀhadꢀnoꢀobviousꢀeffectꢀ
onꢀtheꢀenantioselectivityꢀduringꢀrecyclingꢀ(Fig.ꢀ4).ꢀ
[
10] J.ꢀ M.ꢀ Brown,ꢀ S.ꢀ J.ꢀ Cook,ꢀ R.ꢀ Khan,ꢀ Tetrahedron,ꢀ 1986,ꢀ 42,ꢀ 5105–
109.ꢀ
[11] G.ꢀConsiglio,ꢀF.ꢀMorandini,ꢀM.ꢀScalone,ꢀP.ꢀPino,ꢀJ.ꢀOrganomet.ꢀChem.,ꢀ
985,ꢀ279,ꢀ193–202.ꢀ
[12] S.ꢀAkutagawa,ꢀAppl.ꢀCatal.ꢀA,ꢀ1995,ꢀ128,ꢀ171–207.ꢀ
ꢀ
5
4.ꢀ ꢀ Conclusionsꢀ
1
Weꢀsuccessfullyꢀsynthesizedꢀaꢀnewꢀvinyl‐functionalizedꢀchi‐
[
[
[
[
[
13] P.ꢀY.ꢀWang,ꢀX.ꢀLiu,ꢀJ.ꢀYang,ꢀY.ꢀYang,ꢀL.ꢀZhang,ꢀQ.ꢀH.ꢀYang,ꢀC.ꢀLi,ꢀJ.ꢀMa‐
ralꢀ ligandꢀ (S)‐5,5’‐divinyl‐BINAPꢀ andꢀ itsꢀ relatedꢀ chiralꢀ porousꢀ
organicꢀpolymers.ꢀAfterꢀimpregnatingꢀwithꢀRhꢀspecies,ꢀtheꢀpo‐
rousꢀpolymericꢀcatalystsꢀwithꢀchiralꢀnanopocketsꢀwereꢀappliedꢀ
inꢀtheꢀheterogeneousꢀasymmetricꢀhydroformylationꢀofꢀstyrene.ꢀ
Encouragingly,ꢀ theꢀ enantioselectivityꢀ ofꢀ Rh/Poly‐1ꢀ wasꢀ 1.67ꢀ
timesꢀhigherꢀthanꢀthatꢀofꢀtheꢀhomogeneousꢀanalogue.ꢀThisꢀen‐
hancementꢀofꢀenantioselectivityꢀcouldꢀbeꢀattributedꢀtoꢀtheꢀin‐
troductionꢀ ofꢀ theꢀ flexibleꢀ chiralꢀ nanopockets.ꢀ Furthermore,ꢀ
withꢀ excellentꢀ activityꢀ andꢀ recyclability,ꢀ theꢀ easilyꢀ preparedꢀ
BINAP‐basedꢀ chiralꢀ porousꢀ organicꢀ polymericꢀ catalystꢀ mayꢀ
haveꢀfurtherꢀapplicationsꢀinꢀtheꢀindustrialꢀproductionꢀofꢀchiralꢀ
aldehydesꢀ andꢀ otherꢀ fineꢀ chemicals.ꢀ Otherꢀ efficientꢀ heteroge‐
neousꢀasymmetricꢀcatalyticꢀsystemsꢀforꢀtheꢀproductionꢀofꢀfineꢀ
chemicalsꢀareꢀbeingꢀdevelopedꢀinꢀourꢀlaboratory.ꢀ
ter.ꢀChem.,ꢀ2009,ꢀ19,ꢀ8009–8014.ꢀ
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GraphicalꢀAbstractꢀ
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PorousꢀRh/BINAPꢀpolymersꢀasꢀefficientꢀheterogeneousꢀcatalystsꢀ
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ꢀ
DalianꢀInstituteꢀofꢀChemicalꢀPhysics,ꢀChinesꢀAcademyꢀofꢀSciences;
ꢀ
UniversityꢀofꢀChineseꢀAcademyꢀofꢀSciences;XiamenꢀUniversity;ꢀ
ShanghaiꢀInstituteꢀofꢀAppliedꢀPhysics,ꢀChinesꢀAcademyꢀofꢀSciencesꢀ
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theꢀ correspondingꢀ homogeneousꢀ complexꢀ owingꢀ toꢀ theꢀ presenceꢀ ofꢀ
flexibleꢀchiralꢀnanopockets.ꢀ

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