Photoredox-catalyzed hydrosulfonylation reaction of electron-deficient alkenes with substituted Hantzsch esters and sulfur dioxide

Article abstract of DOI:10.1039/c9cc03004b

A sulfonylation reaction of 4-substituted Hantzsch esters, DABCO·(SO₂)₂, and electron-deficient alkenes at room temperature in the presence of photoredox catalysis under visible light irradiation is described. Not only (E)-chalcones but also (vinylsulfonyl)benzene and 2-vinylpyridine are all suitable substrates in the transformation. This sulfonylation reaction under mild conditions shows a broad substrate scope with a good functional group compatibility. A plausible mechanism is proposed, which shows that the 4-substituted Hantzsch esters would be radical reservoirs under photoredox catalysis. The alkyl radical generated in situ from the 4-substituted Hantzsch ester would be trapped by sulfur dioxide to produce an alkylsulfonyl radical, which would then undergo further transformation leading to the final outcome.

Full text of DOI:10.1039/c9cc03004b

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Reactivity differences of Sc
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DOI: 10.1039/C9CC03004B
ChemCommꢀ
COMMUNICATIONꢀ
ꢀ
Photoredox-catalyzedꢀhydrosulfonylationꢀreactionꢀofꢀelectron-
deficientꢀalkenesꢀwithꢀsubstitutedꢀHantzschꢀestersꢀandꢀsulfurꢀ
dioxideꢀꢀ
unReceivedꢀ00thꢀJanuaryꢀ20xx,ꢀ
Acceptedꢀ00thꢀJanuaryꢀ20xxꢀ
a
b
c
b
a,d
XuefengꢀWang, ꢀMinꢀYang, ꢀWenlinꢀXie, ꢀXiaonaꢀFan,* ꢀandꢀJieꢀWu* ꢀ
DOI:ꢀ10.1039/x0xx00000xꢀ
2 2
Aꢀ sulfonylationꢀ reactionꢀ ofꢀ ofꢀ 4-substitutedꢀ Hantzschꢀ esters,ꢀ DABCO·(SO ) ,ꢀ andꢀ electron-deficientꢀ alkenesꢀ atꢀ roomꢀ
ꢀ
www.rsc.org/ꢀ
temperatureꢀinꢀtheꢀpresenceꢀof photoredoxꢀcatalysisꢀunderꢀvisibleꢀlightꢀirradiationꢀisꢀdescribed.ꢀNotꢀonlyꢀ(E)-chalconesꢀbutꢀ
alsoꢀ(vinylsulfonyl)benzeneꢀandꢀ2-vinylpyridineꢀareꢀallꢀsuitableꢀsubstratesꢀinꢀtheꢀtransformation.ꢀThisꢀsulfonylationꢀreactionꢀ
underꢀmildꢀconditionsꢀshowsꢀbroadꢀsubstrateꢀscopeꢀwithꢀgoodꢀfunctionalꢀgroupꢀcompatibility.ꢀAꢀplausibleꢀmechanismꢀisꢀ
proposed,ꢀwhichꢀshowsꢀthatꢀ4-substitutedꢀHantzschꢀestersꢀwouldꢀbeꢀtheꢀradicalꢀreservoirsꢀunderꢀphotoredoxꢀcatalysis.ꢀTheꢀ
alkylꢀradicalꢀgeneratedꢀinꢀsituꢀfromꢀ4-substitutedꢀHantzschꢀesterꢀwouldꢀbeꢀtrappedꢀbyꢀsulfurꢀdioxideꢀtoꢀproduceꢀalkylsulfonylꢀ
radical,ꢀwhichꢀwouldꢀthenꢀundergoꢀfurtherꢀtransformationꢀleadingꢀtoꢀtheꢀfinalꢀoutcome.ꢀ
1
Theꢀsulfonylꢀunitꢀcanꢀbeꢀfoundꢀbroadlyꢀinꢀpharmaceuticals ꢀandꢀ sulfonylationꢀ reactionsꢀ withꢀ theꢀ insertionꢀ ofꢀ sulfurꢀ dioxideꢀ
2
agrochemicals. ꢀSoꢀfar,ꢀvariousꢀapproachesꢀhaveꢀbeenꢀappearedꢀ throughꢀradicalꢀprocesses ꢀandꢀtheꢀchemistryꢀofꢀ4-substitutedꢀ
4
3
ꢀ
10,11
forꢀ theꢀ preparationꢀ ofꢀ sulfonylꢀ compounds. ꢀ Inꢀ theꢀ pastꢀ fewꢀ Hantzschꢀestersꢀunder photoredoxꢀcatalysis,
years,ꢀgenerationꢀofꢀsulfonylꢀcompoundsꢀthroughꢀtheꢀinsertionꢀ thatꢀtheꢀsulfonatedꢀCardamoninꢀderivativesꢀwouldꢀbeꢀformedꢀ
ꢀweꢀenvisionedꢀ
4
-6
ofꢀsulfurꢀdioxideꢀhasꢀbeenꢀregardedꢀasꢀanꢀattractiveꢀpathway.
ꢀ
fromꢀaꢀreactionꢀofꢀ4-substitutedꢀHantzschꢀesters,ꢀsulfurꢀdioxide,ꢀ
7
Amongꢀ theꢀ methodsꢀ developedꢀ byꢀ usingꢀ DABCO·(SO ) ꢀ orꢀ andꢀ electron-deficientꢀ alkenesꢀ underꢀ visibleꢀ lightꢀ irradiationꢀ
2 2
8
inorganicꢀsulfites ꢀasꢀtheꢀsulfurꢀdioxideꢀsurrogates,ꢀrecentꢀfocusꢀ (Schemeꢀ 1).ꢀ Weꢀ postulatedꢀ thatꢀ alkylꢀ radicalꢀ wouldꢀ beꢀ
ꢀ
hasꢀ beenꢀ centeredꢀ onꢀ theꢀ radicalꢀ processꢀ involvingꢀ sulfonylꢀ generatedꢀ fromꢀ 4-substitutedꢀ Hantzschꢀ estersꢀ under
radicals.ꢀ Althoughꢀ aryldiazoniumꢀ tetrafluoroborates,ꢀ arylꢀ photoredoxꢀcatalysis,ꢀwhichꢀwouldꢀcombineꢀwithꢀsulfurꢀdioxideꢀ
halides,ꢀ andꢀ diaryliodoniumꢀ saltsꢀ haveꢀ beenꢀ usedꢀ asꢀ theꢀ arylꢀ toꢀ provideꢀ sulfonylꢀ radicalꢀ intermediate.ꢀ Furtherꢀ additionꢀ toꢀ
4
radicalꢀsourceꢀwithꢀtheꢀinsertionꢀofꢀsulfurꢀdioxide, ꢀfewꢀreportsꢀ electron-deficientꢀ alkeneꢀ wouldꢀ produceꢀ theꢀ sulfonatedꢀ
9
areꢀ disclosedꢀ fromꢀ alkylꢀ radicalꢀ precursors. ꢀ Recently,ꢀ 4- Cardamoninꢀderivatives.ꢀHerein,ꢀweꢀreportꢀanꢀexampleꢀforꢀtheꢀ
ꢀ
substitutedꢀ Hantzschꢀ estersꢀ inꢀ theꢀ presenceꢀ of photoredoxꢀ sulfonylationꢀreactionꢀofꢀ4-substitutedꢀHantzschꢀesters,ꢀsulfurꢀ
catalystꢀunderꢀvisibleꢀlightꢀirradiationꢀhaveꢀbeenꢀreportedꢀasꢀtheꢀ dioxide,ꢀandꢀelectron-deficientꢀalkenesꢀatꢀroomꢀtemperatureꢀinꢀ
1
0,11
ꢀ
alkylꢀ radicalꢀ reservoirs.
ꢀ Forꢀ example,ꢀ photocatalyticꢀ theꢀ presenceꢀ of photoredoxꢀ catalysisꢀ underꢀ visibleꢀ lightꢀ
Notꢀ onlyꢀ (E)-chalconesꢀ butꢀ alsoꢀ
-substitutedꢀHantzschꢀestersꢀcouldꢀbeꢀachievedꢀinꢀtheꢀabsenceꢀ (vinylsulfonyl)benzeneꢀ andꢀ 2-vinylpyridineꢀ areꢀ allꢀ suitableꢀ
hydroalkylationꢀorꢀdialkylationꢀreactionsꢀofꢀvariousꢀalkenesꢀwithꢀ irradiation.ꢀ
4
1
0bꢀ
ofꢀanꢀexternalꢀelectronꢀacceptor.
ꢀ
antioxidative,ꢀ
substratesꢀ inꢀ theꢀ transformation.ꢀ Thisꢀ sulfonylationꢀ reactionꢀ
Cardamonin,ꢀaꢀnaturalꢀoccurringꢀproduct,ꢀshowsꢀremarkableꢀ underꢀmildꢀconditionsꢀshowsꢀbroadꢀsubstrateꢀscopeꢀwithꢀgoodꢀ
anti-inflammatory,ꢀ
anti-cancer,ꢀ
andꢀ functionalꢀ groupꢀ compatibility.ꢀ Aꢀ plausibleꢀ mechanismꢀ isꢀ
1
2
neuroprotectiveꢀactivities. ꢀAsꢀourꢀcontinuousꢀinterestꢀinꢀtheꢀ proposed,ꢀ whichꢀ showsꢀ thatꢀ 4-substitutedꢀ Hantzschꢀ estersꢀ
synthesisꢀ ofꢀ sulfonatedꢀ naturalꢀ product-likeꢀ compounds,ꢀ weꢀ wouldꢀbeꢀtheꢀradicalꢀreservoirsꢀunderꢀphotoredoxꢀcatalysis.ꢀTheꢀ
conceivedꢀ thatꢀ theꢀ generationꢀ ofꢀ sulfonatedꢀ Cardamoninꢀ alkylꢀradicalꢀgeneratedꢀinꢀsituꢀfromꢀ4-substitutedꢀHantzschꢀesterꢀ
derivativesꢀ wouldꢀ beꢀ beneficialꢀ forꢀ theꢀ subsequentꢀ biologicalꢀ wouldꢀ beꢀ trappedꢀ byꢀ sulfurꢀ dioxideꢀ toꢀ produceꢀ alkylsulfonylꢀ
evaluations.ꢀ Encouragedꢀ byꢀ theꢀ recentꢀ advancesꢀ inꢀ theꢀ radical,ꢀ whichꢀ wouldꢀ thenꢀ undergoꢀ furtherꢀ transformationꢀ
leadingꢀtoꢀtheꢀfinalꢀoutcome.ꢀ
SO
2
alkyl
OMe O
Cardamonin
HO
OH
R
E
E
O
R
PC (cat.)
O O
2
S
+
SO
2
+
R1
R2
hν
R1
R2
N
H
1
2
3
ꢀ
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e
Schemeꢀ 1.ꢀ Aꢀ proposedꢀ routeꢀ forꢀ theꢀ sulfonylationꢀ reactionꢀ ofꢀ 4- Hantzschꢀ estersꢀ 1aꢀ (0.3ꢀ mmol,ꢀ 1.5ꢀ equiv).ꢀ ꢀ Isolatedꢀ yield.ꢀ ꢀ Inꢀ theꢀ
f
View Article Online
DOI: 10.1039/C9CC03004B
2 2
) ꢀ(0.4ꢀmmol,ꢀ2.0ꢀequiv).ꢀ
substitutedꢀ Hantzschꢀ esters,ꢀ sulfurꢀ dioxide,ꢀ andꢀ electron-deficientꢀ presenceꢀofꢀDABCO·(SO
alkenesꢀ
Toꢀ demonstrateꢀ theꢀ aboveꢀ hypothesis,ꢀ weꢀ beganꢀ ourꢀ
investigationsꢀbyꢀstudyingꢀtheꢀreactionꢀofꢀ4-cyclohexylꢀHantzschꢀ subsequentlyꢀexaminedꢀtheꢀgeneralityꢀofꢀtheꢀmethod.ꢀTheꢀresultꢀ
esterꢀ 1a,ꢀ DABCO·(SO ,ꢀ andꢀ (E)-chalconeꢀ 2aꢀ (Tableꢀ 1).ꢀ Weꢀ isꢀ shownꢀ inꢀ Schemeꢀ 2.ꢀ Underꢀ photoirradiationꢀ conditions,ꢀ aꢀ
expectedꢀ thatꢀ alkylꢀ radicalꢀ intermediateꢀ wouldꢀ beꢀ generatedꢀ rangeꢀofꢀ -unsaturatedꢀketonesꢀwasꢀsuccessfullyꢀconvertedꢀ
fromꢀ 4-substitutedꢀ Hantzschꢀ esterꢀ underꢀ photoirradiationꢀ intoꢀtheꢀcorrespondingꢀsulfonated compoundsꢀ .ꢀNotably,ꢀnitro,ꢀ
ꢀ
ꢀ
Withꢀ theꢀ aboveꢀ successfulꢀ conditionsꢀ inꢀ hand,ꢀ weꢀ
2 2
)
α,β
3
ꢀ
conditions.ꢀ Thus,ꢀ photoredoxꢀ catalystꢀ ofꢀ Eosinꢀ Yꢀ wasꢀ initiallyꢀ hydroxyl,ꢀbromo,ꢀchloro,ꢀandꢀmethoxy-containingꢀsubstituentsꢀ
employedꢀ inꢀ 1,2-dichloroethaneꢀ (DCE)ꢀ underꢀ visibleꢀ lightꢀ wereꢀallꢀtoleratedꢀunderꢀtheꢀstandardꢀconditions.ꢀForꢀexample,ꢀ
irradiationꢀ (35ꢀ Wꢀ whiteꢀ CFL)ꢀ atꢀ roomꢀ temperatureꢀ (Tableꢀ 1,ꢀ theꢀnitro-substitutedꢀcompoundꢀ3dꢀwasꢀgeneratedꢀinꢀ43%ꢀyield,ꢀ
entryꢀ 1).ꢀ Gratifyingly,ꢀ theꢀ correspondingꢀ productꢀ 3aꢀ wasꢀ andꢀtheꢀhydroxyl-containingꢀproductꢀ3eꢀwasꢀobtainedꢀinꢀ64%ꢀ
2 2
producedꢀinꢀ41%ꢀyield.ꢀNoꢀreactionꢀoccurredꢀinꢀtheꢀdarkꢀorꢀinꢀ yield.ꢀReactionꢀofꢀ4-cyclohexylꢀHantzschꢀesterꢀ1a,ꢀDABCO·(SO ) ,ꢀ
theꢀabsenceꢀofꢀphotocatalystꢀ(dataꢀnotꢀshownꢀinꢀTableꢀ1).ꢀNoꢀ andꢀ(E)-4-phenylbut-3-en-2-oneꢀwasꢀeffectiveꢀasꢀwell,ꢀgivingꢀriseꢀ
betterꢀresultsꢀwereꢀobservedꢀwhenꢀtheꢀreactionꢀwasꢀperformedꢀ toꢀtheꢀdesiredꢀproductꢀ3kꢀinꢀ60%ꢀyield.ꢀWeꢀfurtherꢀexaminedꢀtheꢀ
inꢀotherꢀsolventsꢀ(Tableꢀ1,ꢀentriesꢀ2-4).ꢀTheꢀyieldꢀofꢀproductꢀ3a
wasꢀincreasedꢀtoꢀ48%ꢀwhenꢀtheꢀreactionꢀtimeꢀwasꢀprolongedꢀtoꢀ DABCO·(SO
8ꢀ hoursꢀ (Tableꢀ 1,ꢀ entryꢀ 5).ꢀ Otherꢀ photocatalystsꢀ wereꢀ thenꢀ workedꢀ well,ꢀ leadingꢀ toꢀ theꢀ correspondingꢀ productsꢀ inꢀ goodꢀ
ꢀ
reactionsꢀ ofꢀ otherꢀ 4-substitutedꢀ Hantzschꢀ estersꢀ
1ꢀ
2 2
)
,ꢀwithꢀ(E)-chalconeꢀ2a.ꢀAsꢀexpected,ꢀallꢀreactionsꢀ
4
screenedꢀ (Tableꢀ 1,ꢀ entriesꢀ 6-9),ꢀ andꢀ itꢀ wasꢀ foundꢀ thatꢀ theꢀ yields.ꢀꢀ
R
reactionꢀ workedꢀ efficientlyꢀ whenꢀ 4-CzIPNꢀ wasꢀ usedꢀ (Tableꢀ 1,ꢀ
EtOOC
entryꢀ7).ꢀTheꢀyieldꢀcouldꢀnotꢀbeꢀimprovedꢀwhenꢀtheꢀreactionꢀ
DABCO (SO
2 2
)
COOEt
R
4CzIPN (3 mol %)
DCE, rt
O O S
2
+
O
timeꢀwasꢀprolongedꢀtoꢀ72ꢀhoursꢀ(Tableꢀ1,ꢀentryꢀ10).ꢀTheꢀresultꢀ
wasꢀ inferiorꢀ whenꢀ theꢀ lightꢀ sourceꢀ wasꢀ changedꢀ toꢀ blueꢀ LEDꢀ
N
H
R1
R2
R1
R2 35 W white CFL
1
2
3
(
Tableꢀ 1,ꢀ entryꢀ 11).ꢀ Aꢀ higherꢀ yieldꢀ wasꢀ furnishedꢀ whenꢀ theꢀ
amountꢀofꢀ4-cyclohexylꢀHantzschꢀesterꢀ1aꢀwasꢀincreasedꢀ(Tableꢀ
,ꢀentryꢀ12).ꢀHowever,ꢀtheꢀyieldꢀcouldꢀnotꢀbeꢀfurtherꢀimprovedꢀ
byꢀchangingꢀtheꢀamountꢀofꢀDABCO·(SO 2ꢀ(Tableꢀ1,ꢀentryꢀ13).ꢀ
Tableꢀ1.ꢀInitialꢀstudiesꢀforꢀtheꢀreactionꢀofꢀ4-cyclohexylꢀHantzschꢀesterꢀ1a,ꢀ
Cy
Cy
Cy
Cy
O O
2
S
O O
2
S
O O
2
S
O O
2
S
1
Ph
Ph p-Tol
Ph Ph
p-Tol Ph
6 4 2
C H p-NO
2
)
3
a, 80%
3b, 74%
3c, 76%
3d, 43%
Cy
Cy
Cy
aꢀ
O O
2
S
O O
2
S
2
O O S
2 2
DABCO·(SO ) ,ꢀandꢀ(E)-chalconeꢀ2aꢀ
Cy
p-OHC H
Ph
p-BrC H
Ph
Ph
C H m-Cl
6
4
6
4
6
4
DABCO (SO
2 2
)
EtOOC
COOEt
3
e, 64%
3f, 50%
3g, 43%
N
N
+
O
Cy
Cy
Cy
N
H
NC
N
CN
N
O O S
O O S
O O S
2
2
2
Ph
Ph
1
a
2a
p-OMeC
6
H
4
Ph Ph
C
6
H
4
o-OMe Ph
C
6
H
4
p-OMe
Cy
Ph
3h, 70%
3i, 50%
3j, 70%
PC (3 mol %)
solvent
2
O O S
Ph
3
5 W white CFL
O O
2
S
O O
2
S
O O
2
S
2
O O S
ꢀ
3
a
4-CzIPN
H
3
C
Ph
Ph
Ph
Ph
Ph
Ph
Ph
3
k, 60%
3l, 81%
3m, 77%
3n, 80%
b
Yieldꢀ(%) ꢀ
Entryꢀ
PCꢀ
Solventꢀ
DCEꢀ
Timeꢀ(h)ꢀ
O
1
2
3
ꢀ
ꢀ
ꢀ
EosinꢀYꢀ
EosinꢀYꢀ
EosinꢀYꢀ
24ꢀ
24ꢀ
24ꢀ
41ꢀ
O
2
O O S
DMFꢀ
26ꢀ
2
O O S
MeCNꢀ
24ꢀ
Ph
Ph
Ph
Ph
3
o, 70%
3p, 70%
4
5
6
7
8
9
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
EosinꢀYꢀ
EosinꢀYꢀ
EosinꢀBꢀ
4-CzIPNꢀ
MeOHꢀ
DCEꢀ
DCEꢀ
DCEꢀ
DCEꢀ
DCEꢀ
DCEꢀ
DCEꢀ
DCEꢀ
DCEꢀ
24ꢀ
48ꢀ
48ꢀ
48ꢀ
48ꢀ
48ꢀ
72ꢀ
48ꢀ
48ꢀ
48ꢀ
32ꢀ
48ꢀ
42ꢀ
77ꢀ
40ꢀ
56ꢀ
78ꢀ
65ꢀ
ꢀ
Schemeꢀ2.ꢀScopeꢀexplorationꢀforꢀtheꢀreactionꢀofꢀ4-substitutedꢀHantzschꢀ
esterꢀ ,ꢀDABCO·(SO ,ꢀandꢀalkeneꢀ .ꢀ
Subsequently,ꢀweꢀexploredꢀtheꢀsulfonylationꢀofꢀCardamoninꢀ
withꢀ 4-cyclohexylꢀ Hantzschꢀ esterꢀ 1aꢀ andꢀ DABCO·(SO ꢀ underꢀ
1
2
)
2
2
ꢀ
Ir(ppy)
3
ꢀ
2 2
)
Ru(bpy) Cl ·6H Oꢀ
3
2
2
theꢀ standardꢀ conditions.ꢀ Asꢀ expected,ꢀ theꢀ correspondingꢀ
productꢀ3qꢀwasꢀaffordedꢀinꢀ69%ꢀyieldꢀ(Schemeꢀ3,ꢀeqnꢀa).ꢀThisꢀ
resultꢀ wasꢀ interesting,ꢀ whichꢀ indicatedꢀ thatꢀ aꢀ wideꢀ rangeꢀ ofꢀ
sulfonatedꢀ Cardamoninꢀ derivativesꢀ couldꢀ beꢀ obtainedꢀ forꢀ
variousꢀ biologicalꢀ evaluations.ꢀ Subsequently,ꢀ aꢀ controlꢀ
experimentꢀ wasꢀ performedꢀ forꢀ theꢀ reactionꢀ ofꢀ 4-cyclohexylꢀ
1
0ꢀ
4-CzIPNꢀ
4-CzIPNꢀ
4-CzIPNꢀ
4-CzIPNꢀ
c
1 ꢀ
1
1
d
e
2 ꢀ
d,f
3 ꢀ
92ꢀ(80) ꢀ
1
87ꢀ
a
Reactionꢀconditions:ꢀ4-cyclohexylꢀHantzschꢀestersꢀ1aꢀ(0.24ꢀmmol,ꢀ1.2ꢀ
equiv),ꢀDABCO·(SO ꢀ(0.3ꢀmmol,ꢀ1.5ꢀequiv),ꢀ(E)-chalconeꢀ2aꢀ(0.2ꢀmmol,ꢀ
.0ꢀequiv),ꢀphotocatalystꢀ(3ꢀmolꢀ%),ꢀsolventꢀ(3.0ꢀmL),ꢀroomꢀtemperature,ꢀ
2 2
)
Hantzschꢀesterꢀ1a,ꢀ(E)-chalconeꢀ2a,ꢀandꢀDABCO·(SO
additionꢀ ofꢀ 2,2,6,6-tetramethyl-1-piperidinyloxyꢀ (TEMPO)ꢀ
Schemeꢀ3,ꢀeqnꢀb).ꢀConsequently,ꢀaꢀtraceꢀamountꢀofꢀproductꢀ3a
2 2
) ꢀwithꢀtheꢀ
1
b
1
N
2
.ꢀ ꢀ HꢀNMRꢀyieldꢀusingꢀ1,3,5-trimethoxybenzeneꢀasꢀinternalꢀstandard.ꢀ
c
d
TheꢀlightꢀwasꢀchangedꢀtoꢀblueꢀLED.ꢀ ꢀInꢀtheꢀpresenceꢀofꢀ4-cyclohexylꢀ
(
ꢀ
ꢀ
2
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
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ꢀ
R
wasꢀ detected,ꢀ whichꢀ revealedꢀ thatꢀ theꢀ transformationꢀ wouldꢀ
proceedꢀthroughꢀaꢀradicalꢀprocess.ꢀꢀ
View Article Online
DOI: 10.1039/C9CC03004B
R
E
E
E
E
O O2S
1
Cy
a)
R1
R2
N
H
Cy
- H
N
OMe O
EtOOC
COOEt
OMe O
O
2
S
3
PC*
E
E
4
-CzIPN (3 mol %)
hν
Ph
Ph
1
a
+
N
H
+
R
S
DCE, rt
H
HO
b)
OH
HO
5 W white CFL
OH
q, 69%
N
H
3
DABCO (SO
2
)
2
PC-
SO
2
PC
Cardamonin
3
O
O
R
R
Cy
O
O O2S
O O2S
O
R
EtOOC
COOEt
Cy
Ph
Ph
Ph 4-CzIPN (3 mol %)
DCE, rt
O
O
2
S
R1
R2
R1
R2
R1
R2
+
2
a
B
A
2
N
H
Ph
ꢀ
DABCO (SO2)2
35 W white CFL
1
a
3a, trace
TEMPO (2.0 equiv)
ꢀ
Schemeꢀ 5.ꢀ Plausibleꢀ mechanismꢀ forꢀ theꢀ reactionꢀ ofꢀ 4-substitutedꢀ
Hantzschꢀesterꢀ ,ꢀDABCO·(SO ,ꢀandꢀalkeneꢀ
Inꢀconclusion,ꢀweꢀhaveꢀdevelopedꢀaꢀsulfonylationꢀreactionꢀofꢀ
ofꢀ4-substitutedꢀHantzschꢀesters,ꢀDABCO·(SO ,ꢀandꢀelectron-
1
2
)
2
2ꢀ
Schemeꢀ3.ꢀFurtherꢀexploration
Theꢀaboveꢀmethodꢀwasꢀfurtherꢀextendedꢀtoꢀotherꢀalkenes.ꢀ
Forꢀ instance,ꢀ sulfonylationꢀ reactionꢀ ofꢀ 4-cyclohexylꢀ Hantzschꢀ
ꢀ
ꢀ
ꢀ
2 2
)
ꢀ
deficientꢀ alkenesꢀ atꢀ roomꢀ temperatureꢀ inꢀ theꢀ presenceꢀ of
photoredoxꢀcatalysisꢀunderꢀvisibleꢀlightꢀirradiation.ꢀNotꢀonlyꢀ(E)-
esterꢀ1a,ꢀDABCO·(SO
2 2
) ꢀandꢀ(vinylsulfonyl)benzeneꢀaffordedꢀtheꢀ
correspondingꢀ productꢀ
conditionsꢀ(Schemeꢀ4,ꢀeqnꢀa).ꢀ2-Vinylpyridineꢀwasꢀalsoꢀaꢀsuitableꢀ
4
ꢀ inꢀ 42%ꢀ yieldꢀ underꢀ theꢀ standardꢀ
chalconesꢀ butꢀ alsoꢀ (vinylsulfonyl)benzeneꢀ andꢀ 2-vinylpyridineꢀ
areꢀ allꢀ suitableꢀ substratesꢀ inꢀ theꢀ transformation.ꢀ Reactionꢀ ofꢀ
Cardamoninꢀ isꢀ workableꢀ asꢀ well.ꢀ Thisꢀ sulfonylationꢀ reactionꢀ
underꢀmildꢀconditionsꢀshowsꢀbroadꢀsubstrateꢀscopeꢀwithꢀgoodꢀ
functionalꢀ groupꢀ compatibility.ꢀ Aꢀ plausibleꢀ mechanismꢀ isꢀ
proposed,ꢀ whichꢀ showsꢀ thatꢀ 4-substitutedꢀ Hantzschꢀ estersꢀ
wouldꢀbeꢀtheꢀradicalꢀreservoirsꢀunderꢀphotoredoxꢀcatalysis.ꢀTheꢀ
alkylꢀradicalꢀgeneratedꢀinꢀsituꢀfromꢀ4-substitutedꢀHantzschꢀesterꢀ
wouldꢀ beꢀ trappedꢀ byꢀ sulfurꢀ dioxideꢀ toꢀ produceꢀ alkylsulfonylꢀ
radical,ꢀ whichꢀ wouldꢀ thenꢀ undergoꢀ furtherꢀ transformationꢀ
leadingꢀtoꢀtheꢀfinalꢀoutcome.ꢀꢀ
substrateꢀinꢀtheꢀreactionꢀofꢀ4-cyclohexylꢀHantzschꢀesterꢀ1aꢀwithꢀ
DABCO·(SO
Schemeꢀ4,ꢀeqnꢀb).ꢀTheꢀcorrespondingꢀproductꢀ6ꢀwasꢀfurnishedꢀ
inꢀ 38%ꢀ yieldꢀ whenꢀ benzylꢀ acrylateꢀ wasꢀ employedꢀ insteadꢀ
Schemeꢀ4,ꢀeqnꢀc).ꢀHowever,ꢀnoꢀreactionꢀoccurredꢀwhenꢀN,N-
2 2
) ,ꢀleadingꢀtoꢀtheꢀexpectedꢀproductꢀ5ꢀinꢀ30%ꢀyieldꢀ
(
(
dimethylacrylamideꢀorꢀacrylonitrileꢀwasꢀusedꢀasꢀtheꢀsubstrate.ꢀ
Aꢀtraceꢀamountꢀofꢀproductꢀwasꢀdetectedꢀwhenꢀ4-vinylpyridineꢀ
wasꢀutilizedꢀasꢀtheꢀpartner.ꢀ
a)
Cy
2 2
DABCO (SO )
EtOOC
COOEt
4
-CzIPN (3 mol %)
O
O
+
S
DCE, rt
35 W white CFL
Cy
2
SO Ph
N
H
2
SO Ph
1
a
4, 42%
Conflictsꢀofꢀinterestꢀ
b)
Cy
DABCO (SO
2 2
)
EtOOC
COOEt
O
O
4
-CzIPN (3 mol %)
S
+
Cy
Thereꢀareꢀnoꢀconflictsꢀtoꢀdeclare.ꢀ
DCE, rt
N
H
N
N
35 W white CFL
1
a
5, 30%
c)
Cy
DABCO (SO
2
)
2
Acknowledgementsꢀ
EtOOC
COOEt
O
O
4
-CzIPN (3 mol %)
S
OBn
O
+
Cy
FinancialꢀsupportꢀfromꢀNationalꢀNaturalꢀScienceꢀFoundationꢀofꢀ
Chinaꢀ (Nos.ꢀ 21871053ꢀ andꢀ 21532001)ꢀ isꢀ gratefullyꢀ
acknowledged.ꢀ
OBn
DCE, rt
35 W white CFL
N
H
1
a
O
6, 38%
ꢀ
Schemeꢀ4.ꢀReactionsꢀofꢀ4-cyclohexylꢀHantzschꢀesterꢀ1a,ꢀDABCO·(SO
andꢀotherꢀalkenes
Onꢀtheꢀbasisꢀofꢀtheꢀaboveꢀresultsꢀcombinedꢀwithꢀpreviousꢀ
2 2
) ,ꢀ
ꢀ
Notesꢀandꢀreferencesꢀ
ꢀ
1
.
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