Nucleophile dependent formation of 6- and 7-membered: N -heterocycles by platinum-catalysed cyclisation of 1,5-bisallenes

Article abstract of DOI:10.1039/c7ob01469d

An unprecedented Pt-catalysed cyclisation of N-tethered 1,5-bisallenes in the presence of oxygen nucleophiles is reported, where formation of 6- or 7-membered rings is driven by the choice of nucleophile and the mechanism dictated by the nucleophile and the electronic properties of the bisallene. The reaction in the presence of alcohols gives preferentially vinyltetrahydropyridines with an extra alkoxy group and Pt-H as the active species in the catalytic cycle, while formation of di- and tetrahydroazepines with an extra hydroxyl group is favoured when water is used as nucleophile, via nucleophilic attack/carbocyclization as the favoured pathway. The products obtained are frequently found in the core of natural products with important biological activities, so understanding this complex mechanistic behaviour and exploiting this new methodology will have a big impact in organic synthesis and organometallic chemistry.

Full text of DOI:10.1039/c7ob01469d

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January 2016 Pages 1–372
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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
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Organic & Biomolecular Chemistry
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DOI: 10.1039/C7OB01469D
JournalꢀNameꢀ
COMMUNICATIONꢀ
ꢀ
NucleophileꢀDependentꢀFormationꢀofꢀ6-ꢀandꢀ7-MemberedꢀN-
HeterocyclesꢀbyꢀPlatinum-CatalysedꢀCyclisationꢀofꢀ1,5-Bisallenesꢀꢀ
Receivedꢀ00thꢀJanuaryꢀ20xx,ꢀ
Acceptedꢀ00thꢀJanuaryꢀ20xxꢀ
[
a]
[a]
[a]
MaríaꢀTeresaꢀQuirós, ꢀCésarꢀHurtado-Rodrigo, ꢀMaríaꢀPazꢀMuñoz*
DOI:ꢀ10.1039/x0xx00000xꢀ
www.rsc.org/ꢀ
[
4a,ꢀ 5]
Anꢀ unprecedentedꢀ Pt-catalysedꢀ cyclisationꢀ ofꢀ N-tetheredꢀ 1,5- catalysedꢀ cyclisation.
ꢀ Interestingly,ꢀ formationꢀ ofꢀ 6-
bisallenesꢀ inꢀ theꢀ presenceꢀ ofꢀ oxygenꢀ nucleophilesꢀ isꢀ reported,ꢀ memberedꢀringsꢀinꢀtheseꢀsystemsꢀhasꢀbeenꢀobservedꢀinꢀRh(I)-
[
6]
[5b]ꢀ
whereꢀformationꢀofꢀ6-ꢀorꢀ7-memberedꢀringsꢀisꢀdrivenꢀbyꢀtheꢀchoiceꢀ catalysedꢀcyclisationꢀwithꢀexternalꢀbis-, ꢀorꢀmono-allenes.
ofꢀnucleophileꢀandꢀtheꢀmechanismꢀdictatedꢀbyꢀtheꢀnucleophileꢀandꢀ Anꢀ unusualꢀ exampleꢀ ofꢀ twistedꢀ head-to-headꢀ [2+2]ꢀ
theꢀ electronicꢀ propertiesꢀ ofꢀ theꢀ bisallene.ꢀ Theꢀ reactionꢀ inꢀ theꢀ cycloadditionꢀ hasꢀ alsoꢀ beenꢀ reportedꢀ usingꢀ gold(I)ꢀ
[
7]
presenceꢀofꢀalcoholsꢀgivesꢀpreferentiallyꢀvinyltetrahydropyridinesꢀ complexes,ꢀlimitedꢀtoꢀN-tetheredꢀ1,5-bisallenes. ꢀꢀ
withꢀanꢀextraꢀalkoxyꢀgroupꢀandꢀPt-Hꢀasꢀtheꢀactiveꢀspeciesꢀinꢀtheꢀ
Followingꢀourꢀinvestigationsꢀintoꢀmetal-catalysedꢀreactionsꢀofꢀ
[8]
allenesꢀ withꢀ nucleophiles, ꢀ weꢀ wereꢀ interestedꢀ inꢀ theꢀ
catalyticꢀcycle,ꢀwhileꢀformationꢀofꢀdi-ꢀandꢀtetrahydroazepinesꢀwithꢀ
anꢀ extraꢀ hydroxylꢀ groupꢀ isꢀ favouredꢀ whenꢀ waterꢀ isꢀ usedꢀ asꢀ
nucleophile,ꢀ viaꢀ nucleophilicꢀ attack/carbocyclizationꢀ asꢀ theꢀ
favouredꢀpathway.ꢀTheꢀproductsꢀobtainedꢀareꢀfrequentlyꢀfoundꢀinꢀ
theꢀcoreꢀofꢀnaturalꢀproductsꢀwithꢀimportantꢀbiologicalꢀactivities,ꢀ
soꢀ understandingꢀ thisꢀ complexꢀ mechanisticꢀ behaviourꢀ andꢀ
exploitingꢀthisꢀnewꢀmethodologyꢀwillꢀhaveꢀaꢀbigꢀimpactꢀinꢀorganicꢀ
synthesisꢀandꢀorganometallicꢀchemistry.ꢀ
platinum-catalysedꢀcyclisationꢀofꢀ1,5-bisallenesꢀinꢀtheꢀpresenceꢀ
ꢀ
ofꢀoxygenꢀnucleophilesꢀ(Schemeꢀ1).
Theꢀ onlyꢀ exampleꢀ reportedꢀ toꢀ dateꢀ ofꢀ incorporationꢀ ofꢀ anꢀ
externalꢀ nucleophileꢀ isꢀ theꢀ Pd(0)-catalysedꢀ cyclisationꢀ ofꢀ 1,5-
bisallenesꢀwithꢀprimaryꢀaminesꢀandꢀorganicꢀhalidesꢀtoꢀgiveꢀ10-
[9,10]
memberedꢀ azacycles.
platinumꢀinꢀtheꢀreactionꢀwithꢀ1,5-bisallenes isꢀscarce.ꢀTheꢀonlyꢀ
ꢀ Onꢀ theꢀ otherꢀ hand,ꢀ theꢀ useꢀ ofꢀ
ꢀ
Alleneꢀ chemistryꢀ inꢀ theꢀ presenceꢀ ofꢀ transitionꢀ metalꢀ reportedꢀexampleꢀisꢀtheꢀreductiveꢀcyclisationꢀofꢀ1,5-bisallenesꢀ
complexesꢀ isꢀ nowadaysꢀ aꢀ veryꢀ importantꢀ topicꢀ thatꢀ catalysedꢀbyꢀaꢀPt-phosphineꢀcomplexꢀinꢀtheꢀpresenceꢀofꢀSnCl2ꢀ
[
11]
underpinsꢀ manyꢀ challengesꢀ andꢀ advancesꢀ inꢀ organicꢀ andꢀH2ꢀtoꢀgiveꢀ5-memberedꢀrings.
ꢀ
[
1]
synthesis. ꢀ Althoughꢀ aꢀ lotꢀ ofꢀ attentionꢀ hasꢀ beenꢀ paidꢀ inꢀ Ourꢀ initialꢀ screeningꢀ usingꢀ PtCl2ꢀ inꢀ MeOHꢀ withꢀ modelꢀ 1,5-
recentꢀ yearsꢀ toꢀ reactionsꢀ involvingꢀ allenes,ꢀ progressꢀ usingꢀ bisalleneꢀ1aꢀgaveꢀbis-acetalꢀ2aꢀbyꢀdoubleꢀdihydroalkoxylationꢀ
[8c]
[12]
non-conjugatedꢀ bisallenesꢀ hasꢀ beenꢀ muchꢀ slowerꢀ dueꢀ toꢀ ofꢀ eachꢀ allene, ꢀ asꢀ wellꢀ asꢀ trieneꢀ3aa, ꢀ andꢀ tracesꢀ ofꢀ twoꢀ
[13]
[14]ꢀ
issuesꢀ controllingꢀ theꢀ selectivityꢀ ofꢀ theꢀ processesꢀ andꢀ theꢀ cyclesꢀ4aa ꢀandꢀ5aaꢀ(Schemeꢀ1). TheꢀuseꢀofꢀaꢀcationicꢀPt-
[
2]
highꢀreactivityꢀofꢀtheseꢀsystems. ꢀInꢀthisꢀarea,ꢀ1,5-bisallenesꢀ complexꢀ underꢀ theꢀ sameꢀ conditionsꢀ avoidedꢀ formationꢀ ofꢀ
haveꢀ shownꢀ toꢀ beꢀ excellentꢀ buildingꢀ blocksꢀ forꢀ transitionꢀ acetalꢀ2a.ꢀInterestingly,ꢀtheꢀoutcomeꢀofꢀtheꢀreactionꢀwasꢀveryꢀ
[
15]
[16]
metal-catalysedꢀ cyclisationsꢀ andꢀ cycloadditions,ꢀ offeringꢀ sensitiveꢀtoꢀreactionꢀconditions,ꢀcatalyst ꢀandꢀnucleophile.
ꢀ
versatileꢀreactivityꢀ(tail-to-tail,ꢀhead-to-headꢀorꢀtail-to-head)ꢀ Mixturesꢀofꢀtrieneꢀ3aaꢀandꢀvinyl-tetrahydropyridineꢀ4aaꢀwithꢀ
forꢀtheꢀconstructionsꢀofꢀcarbo-ꢀandꢀheterocyclesꢀofꢀdifferentꢀ anꢀ extraꢀ methoxyꢀ groupꢀ inꢀ theꢀ finalꢀ skeletonꢀ wereꢀ
sizesꢀ dependingꢀ onꢀ theꢀ metalꢀ employedꢀ andꢀ theꢀ reactionꢀ preferentiallyꢀ obtainedꢀ inꢀ theꢀ reactionꢀ whenꢀ alcoholsꢀ wereꢀ
[
3]
conditions. ꢀ Forꢀ example,ꢀ 5-memberedꢀ ringsꢀ seemꢀ toꢀ beꢀ usedꢀ asꢀ nucleophile,ꢀ withꢀ theꢀ bestꢀ resultsꢀ obtainedꢀ withꢀ aꢀ
[
4]
favoredꢀunderꢀpalladiumꢀcatalysis, ꢀwhileꢀ7-memberedꢀringsꢀ mixtureꢀofꢀꢀTHF:ROHꢀ(10:1)ꢀatꢀ70ºCꢀforꢀ1.5ꢀhꢀ(Rꢀ=ꢀMe,ꢀEt,ꢀPr,ꢀ
haveꢀbeenꢀobtainedꢀfromꢀ1,5-bisallenesꢀbyꢀthermalꢀorꢀRh(I)- Schemeꢀ1).ꢀ
Moreꢀinterestingly,ꢀwhenꢀH2Oꢀwasꢀusedꢀasꢀnucleophileꢀunderꢀ
similarꢀconditions,ꢀweꢀfoundꢀaꢀswitchꢀinꢀtheꢀregioselectivityꢀtoꢀ
formꢀ di-ꢀ andꢀ tetrahydro-1H-azepinesꢀ withꢀ anꢀ extraꢀ hydroxylꢀ
groupꢀ asꢀ theꢀ onlyꢀ cyclesꢀ (5adꢀ andꢀ 6ad,ꢀ Schemeꢀ 1).ꢀ Furtherꢀ
optimizationꢀ revealedꢀ thatꢀ withꢀ theꢀ sameꢀ cationicꢀ platinumꢀ
complexꢀ atꢀ 70ºC,ꢀ aꢀ 1:3ꢀ ratioꢀ ofꢀ THF:H2Oꢀ wasꢀ crucialꢀ toꢀ
selectivelyꢀformꢀcycloheptadienes,ꢀwithoutꢀtracesꢀofꢀtheꢀtriene.ꢀꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ1ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Org aP nl ei ca s&e ꢀ Bd oi oꢀ nmo ot ꢀ lae dc j uu ls at rꢀ mC ahr eg imn si sꢀ try
Page 2 of 8
JournalꢀNameꢀ
ꢀCOMMUNICATIONꢀ
Productsꢀwereꢀnotꢀcompletelyꢀstableꢀtoꢀpurificationꢀbyꢀcolumnꢀ slowꢀreactionsꢀandꢀwhenꢀnoꢀnucleophileꢀwasꢀpres
V
e
ie
n
w
t
A
,ꢀrt
w
icl
h
e
i
O
c
n
h
li
ꢀ
n
i
e
sꢀ
[
11a]
DOI: 10.1039/C7OB01469D
chromatography,ꢀ partlyꢀ explainingꢀ theꢀ lowꢀ isolatedꢀ yieldsꢀ inꢀ agreementꢀ withꢀ resultsꢀ previouslyꢀ reported.
Reactionꢀ
obtained.ꢀ Additionally,ꢀ weꢀ observedꢀ decompositionꢀ ofꢀ theꢀ withꢀonlyꢀAgSbF6ꢀ(10ꢀmol%)ꢀledꢀtoꢀrecoverꢀunreactedꢀstartingꢀ
trieneꢀandꢀtheꢀbisallenesꢀwithꢀcationicꢀplatinumꢀcomplexesꢀinꢀ material.ꢀ
OMe
ROH
•
3
OMe
OMe
OMe
OR TsN
OH
TsN
OH
[Pt(II)]
[Pt(II)]
TsN
TsN
TsN
OR
R = Me, 4aa
R = Et, 4ab
R = Pr, 4ac
TsN
TsN
H
3
solvent,
solvent,
70˚C
R = Me,
Et, Pr
5
aa
7
0˚C
R = Me, 3aa
R = Et, 3ab
R = Pr, 3ac
MeO
6
ad
TsN
5ad
OH
•
R = H
1
a
2
a
PtCl2 (5 mol%), MeOH, 20 h --> 2a : 3aa : 4aa : 5aa, 1(33%) : 1(19%) : 0.2(2%) : 0.2(2%)
Pt]cat, MeOH, 20 h --> 3aa : 4aa : 5aa, 1(25%) : 0.1(11%) : 0.3(13%)
[Pt]cat, THF:MeOH (1:5), 1.5 h --> 3aa : 4aa, 1(22%) : 0.8(18%)
H
[
3
ad
[
[
[
Pt]cat, THF:MeOH (10:1), 1.5 h --> 3aa : 4aa, 1(24%) : 1.2(35%)
Pt]cat, THF:EtOH (10:1), 1.5 h --> 3ab : 4ab, 1(20%) : 1.25(23%)
Pt]cat, THF:PrOH (10:1), 1.5 h --> 3ac : 4ac, 1.36(24%) : 1(20%)
3ad : 5ad : 6ad, 0.09(2%) : 0.8(16%) : 1(21%) <--- [Pt]cat, THF:H O (9:1), 5.5 h
2
5ad : 6ad, 1:9.8(43%)
<--- [Pt]cat, THF:H O (1:3), 12 h
2
ꢀ
Schemeꢀ1.ꢀNucleophileꢀdependentꢀPt-catalysedꢀalkoxy-ꢀorꢀhydroxycyclisationꢀofꢀ1,5-bisallenes.ꢀ[Pt]catꢀ=ꢀPtCl
2
(MeCN)
2
ꢀ(5ꢀmol%)/AgSbF
6
ꢀ(10ꢀmol%).ꢀIsolatedꢀyieldsꢀ(%).ꢀ
Sinceꢀtheꢀunderstandingꢀofꢀtheꢀmechanismꢀcouldꢀhelpꢀtoꢀfindꢀ whichꢀ suggestsꢀ thatꢀ dimericꢀ speciesꢀ ofꢀ platinumꢀ complexesꢀ
[18]
waysꢀofꢀimprovingꢀtheꢀyieldsꢀandꢀselectivityꢀofꢀtheꢀreactionꢀandꢀ couldꢀbeꢀinvolved. ꢀInꢀcontrastꢀtoꢀtheꢀreactionꢀinꢀmethanol,ꢀ
inꢀ orderꢀ toꢀ understandꢀ thisꢀ unexpectedꢀ divergentꢀ reactivityꢀ theꢀbisalleneꢀdisplayedꢀfirstꢀorderꢀkineticsꢀdecayꢀinꢀtheꢀreactionꢀ
encounteredꢀ dependingꢀ onꢀ theꢀ nucleophile,ꢀ weꢀ performedꢀ aꢀ withꢀ waterꢀ andꢀ noꢀ KIE,ꢀ suggestingꢀ differentꢀ mechanismsꢀ areꢀ
mechanisticꢀinvestigationꢀofꢀbothꢀreactionsꢀ(seeꢀSI).ꢀꢀ
operatingꢀwithꢀbothꢀnucleophiles.ꢀ
1
Theꢀkineticꢀexperimentsꢀwereꢀcarriedꢀoutꢀmeasuringꢀ HꢀNMRꢀ
spectraꢀ atꢀ differentꢀ reactionꢀ timesꢀ inꢀ THF-d8:CD3ODꢀ orꢀ THF-
d8:CH3OHꢀ 10:1ꢀ andꢀ THF-d8:D2Oꢀ orꢀ THF-d8:H2Oꢀ 5:1ꢀ atꢀ 50ºCꢀ
X
X
X
X
X
X
X
PtCl
2
(MeCN)
2
(5 mol%),
•
•
OCY
3
AgSbF
6
(10 mol%),
OCY
3
+
TsN
Y
TsN
Y
(
temperatureꢀ limitedꢀ byꢀ theꢀ boilingꢀ pointꢀ ofꢀ THF-d8).ꢀ Anꢀ
TsN
X
THF-d
8
:CY
3
OY (10:1),
inductionꢀperiodꢀwasꢀobservedꢀinꢀallꢀcases,ꢀwhichꢀunexpectedlyꢀ
wasꢀ longerꢀ whenꢀ protonatedꢀ nucleophilesꢀ (CH3OHꢀ andꢀ H2O)ꢀ
X
5
0˚C
X
X
3aa-d
n
4aa-d
n
X
1
a, X = H
wereꢀused.ꢀTheꢀkineticꢀanalysisꢀandꢀtheꢀorderꢀofꢀtheꢀdifferentꢀ 1a-d
4
, X = D
KIE (1a/1a-d
KIE (1a/1a-d
4
4
, CH
, CD
3
3
OH) = 0.62±0.06 (for 3aa); 0.84±0.11 (for 4aa)
OD) = 0.63±0.06 (for 3aa); 1.39±0.09 (for 4aa)
Y = H or D
componentsꢀ wasꢀ measuredꢀ usingꢀ theꢀ initialꢀ ratesꢀ methodꢀ
[17]
KIE (1a, CH
3
OH/CD
3
OD) = 1.75±0.18 (for 3aa); 0.67±0.08 (for 4aa)
OD) = 1.8±0.3 (for 3aa); 1.13±0.19 (for 4aa)
and/orꢀ theꢀ graphicalꢀ methodꢀ afterꢀ theꢀ inductionꢀ period,
usingꢀbisalleneꢀ1aꢀasꢀmodelꢀsubstrate.ꢀ
ꢀ
KIE (1a-d , CH
4
3
OH/CD
3
Theꢀ orderꢀ inꢀ CD3ODꢀ wasꢀ foundꢀ toꢀ beꢀ 1ꢀ forꢀ theꢀ formationꢀ ofꢀ
bothꢀproducts,ꢀtrieneꢀ3aaꢀandꢀcycleꢀ4aa.ꢀInꢀtheꢀreactionꢀwithꢀ
methanolꢀ asꢀ nucleophile,ꢀ theꢀ orderꢀ inꢀ platinumꢀ calculatedꢀ
usingꢀ theꢀ initialꢀ ratesꢀ wasꢀ 1ꢀ forꢀ cycleꢀ 4aa,ꢀ butꢀ couldꢀ notꢀ beꢀ
determinedꢀ forꢀ theꢀ formationꢀ ofꢀ trieneꢀ 3aa.ꢀ Theꢀ graphicalꢀ
methodꢀ(withꢀandꢀwithoutꢀtheꢀinductionꢀperiod)ꢀdidꢀnotꢀgiveꢀ
betterꢀ results,ꢀ suggestingꢀ changesꢀ inꢀ theꢀ catalyticꢀ speciesꢀ inꢀ
unknownꢀ waysꢀ orꢀ aꢀ fastꢀ catalystsꢀ deactivationꢀ process.ꢀ Theꢀ
decayꢀinꢀconcentrationꢀofꢀtheꢀbisalleneꢀfollowedꢀpseudo-zeroꢀ
orderꢀ kinetics,ꢀ suggestingꢀ anꢀ “offꢀ cycle”ꢀ rate-limitingꢀ step.ꢀ
Besides,ꢀ whenꢀ theꢀ reactionꢀ wasꢀ performedꢀ withꢀ theꢀ 1a-d4ꢀ
analogueꢀ (inꢀ CH3OHꢀ andꢀ CD3OD),ꢀ theꢀ consumptionꢀ ofꢀ theꢀ
bisalleneꢀwasꢀfaster,ꢀwithꢀaꢀsecondaryꢀKIEꢀ~ꢀ0.5,ꢀsuggestingꢀaꢀ
•
PtCl
AgSbF
2
(MeCN)
2
(5 mol%),
6
(10 mol%),
OY
OY
TsN
X
+
X
THF-d
8
:Y
2
O (5:1),
2
CH Y
•
50˚C
Y
2
1a
5ad-d
KIE (1a, H
Schemeꢀ2.ꢀLabellingꢀexperimentsꢀandꢀKIEsꢀwithꢀdeuteratedꢀanalogues.ꢀ
2
6ad-d
2
2
O/D O) = 1.19±0.02 (for 6ad)
ꢀ
Theꢀ reactionꢀ usingꢀ deuteratedꢀ nucleophilesꢀ andꢀ deuteratedꢀ
bisalleneꢀ1a-d4ꢀ(TsN-)ꢀunderꢀoptimizedꢀconditionsꢀshowedꢀhighꢀ
incorporationꢀ ofꢀ deuteriumꢀ inꢀ theꢀ productsꢀ atꢀ theꢀ positionsꢀ
ꢀ
shownꢀ inꢀ Schemeꢀ 2ꢀ (seeꢀ SI). KIEsꢀ wereꢀ calculatedꢀ forꢀ allꢀ theꢀ
processesꢀ usingꢀ theꢀ initialꢀ ratesꢀ methodꢀ afterꢀ theꢀ inductionꢀ
period,ꢀ usingꢀ 1aꢀ andꢀ deuteratedꢀ bisalleneꢀ 1a-d4,ꢀ inꢀ theꢀ
presenceꢀofꢀCH3OHꢀorꢀCD3ODꢀandꢀH2OꢀorꢀD2Oꢀ(Schemeꢀ2).ꢀꢀ
2
3
changeꢀinꢀhybridizationꢀfromꢀsp ꢀtoꢀsp ꢀinꢀatꢀleastꢀoneꢀofꢀtheꢀ
terminalꢀcarbonꢀofꢀtheꢀbisalleneꢀinꢀtheꢀturnover-limitingꢀstep.ꢀ
Theꢀkineticꢀmeasurementsꢀusingꢀwaterꢀwereꢀperformedꢀusingꢀ
mixturesꢀofꢀTHF-d8:D2Oꢀ5:1ꢀatꢀ50ºC,ꢀwhichꢀledꢀtoꢀtheꢀformationꢀ
ofꢀ aꢀ smallꢀ amountꢀ ofꢀ trieneꢀ 3ad.ꢀ Dataꢀ obtainedꢀ forꢀ theꢀ
formationꢀofꢀtrieneꢀ3adꢀandꢀcycleꢀ5adꢀinꢀtheꢀreactionꢀwithꢀD2Oꢀ
couldꢀ notꢀ beꢀ analyzedꢀ inꢀ allꢀ cases,ꢀ dueꢀ toꢀ theꢀ lowꢀ
concentrationꢀ ofꢀ theseꢀ products.ꢀ Inꢀ theꢀ reactionꢀ withꢀ water,ꢀ
theꢀorderꢀinꢀplatinumꢀwasꢀ0.5ꢀforꢀtheꢀformationꢀofꢀcycleꢀ6ad,ꢀ
o
TheꢀKIEꢀwasꢀmeasuredꢀinꢀTHF:water,ꢀ10:1ꢀmixturesꢀatꢀ50ꢀ C.ꢀNoꢀ
clearꢀ KIEꢀ (~1)ꢀ wasꢀ observedꢀ whenꢀ D2Oꢀ wasꢀ usedꢀ inꢀ theꢀ
formationꢀofꢀcycleꢀ6adꢀafterꢀtheꢀinductionꢀperiod.ꢀSimilarly,ꢀnoꢀ
clearꢀKIEꢀ(~1)ꢀwasꢀobservedꢀinꢀtheꢀformationꢀofꢀcycleꢀ4aaꢀinꢀtheꢀ
reactionꢀ withꢀ CH3OHꢀ orꢀ CD3ODꢀ withꢀ theꢀ protonatedꢀ orꢀ
deuteratedꢀ bisallenes.ꢀ Interestingly,ꢀ primaryꢀ KIEꢀ ~ꢀ 1.8ꢀ wasꢀ
observedꢀ inꢀ theꢀ formationꢀ ofꢀ trieneꢀ 3aaꢀ whenꢀ CD3ODꢀ wasꢀ
used,ꢀ andꢀ inverseꢀ secondaryꢀ KIEꢀ ~ꢀ 0.63ꢀ wasꢀ observedꢀ inꢀ theꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
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JournalꢀNameꢀ
ꢀCOMMUNICATIONꢀ
lf ,ꢀ
formationꢀ ofꢀ deuteratedꢀ trieneꢀ whenꢀ 1a-d4ꢀ wasꢀ usedꢀ asꢀ ratiosꢀ whenꢀ ED-substituentsꢀ areꢀ presentꢀ inꢀ theꢀ su onamOnidline
View Article e
2
startingꢀmaterial,ꢀsuggestingꢀaꢀchangeꢀinꢀhybridisationꢀfromꢀsp ꢀ whileꢀ theꢀ ratioꢀ ofꢀ 3ꢀ increasesꢀ withꢀ EW-substituentsꢀ andꢀ
DOI: 10.1039/C7OB01469D
3
toꢀ sp ꢀ inꢀ theꢀ turnover-limitingꢀ stepꢀ ofꢀ theꢀ formationꢀ ofꢀ theꢀ cycloheptadienesꢀ5ꢀareꢀalsoꢀobtained.ꢀInꢀwater,ꢀtetrahydro-1H-
[
19]
trieneꢀ(Schemeꢀ2).
ꢀ
azepinesꢀ6ꢀwereꢀtheꢀmajorꢀproductsꢀinꢀallꢀcasesꢀ(Schemeꢀ3).ꢀꢀ
Inꢀorderꢀtoꢀgainꢀmoreꢀinsightꢀintoꢀtheꢀpossibleꢀintermediatesꢀ Toꢀ ourꢀ surpriseꢀ theꢀ Hammettꢀ plotsꢀ obtainedꢀ forꢀ allꢀ productsꢀ
andꢀevaluateꢀhowꢀtheꢀelectronicꢀpropertiesꢀofꢀtheꢀsulfonamideꢀ usingꢀ bothꢀ nucleophilesꢀ showedꢀ aꢀ changeꢀ ofꢀ theꢀ signꢀ ofꢀ theꢀ
group,ꢀ intrinsicallyꢀ aꢀ strongꢀ electron-withdrawingꢀ group,ꢀ slope,ꢀ withꢀ aꢀ concaveꢀ shapeꢀ forꢀ allꢀ theꢀ compoundsꢀ inꢀ bothꢀ
ꢀ
affectedꢀtheꢀreactionꢀoutcome,ꢀweꢀcarriedꢀoutꢀtheꢀreactionsꢀofꢀ reactions. Thisꢀ suggestsꢀ thatꢀ differentꢀ mechanismsꢀ areꢀ
1
,5-bisallenesꢀ withꢀ differentꢀ para-substituentsꢀ inꢀ theꢀ operatingꢀ dependingꢀ onꢀ theꢀ electronicꢀ propertiesꢀ ofꢀ theꢀ
phenylsulfonylꢀ groupꢀ inꢀ methanolꢀ andꢀ waterꢀ underꢀ theꢀ tethersꢀ inꢀ bisallenesꢀ 1ꢀ withꢀ bothꢀ nucleophiles,ꢀ whichꢀ isꢀ
optimizedꢀ conditions.ꢀ Mixturesꢀ ofꢀ trienesꢀ 3ꢀ andꢀ remarkableꢀgivingꢀtheꢀinherentꢀelectron-withdrawingꢀnatureꢀofꢀ
[20]
vinylcyclohexenesꢀ 4ꢀ wereꢀ obtainedꢀ inꢀ methanolꢀ inꢀ similarꢀ theꢀsulfonamideꢀgroupꢀ(Figureꢀ1ꢀandꢀ2).
•
PtCl (MeCN)2 (5 mol%),
AgSbF6 (10 mol%),
PtCl (MeCN) (5 mol%),
AgSbF6 (10 mol%),
2
OR
2
2
OH
OH
OR
+
X
X
XH
+
X
X
THF:ROH (10:1),
THF:H O (1:3),
2
7
0˚C, 1.5 h
7
0˚C, 12 h
•
3
4
1
R = Me, Et, Pr
5
6
X = Ts, R = Me, 5ad + 6ad, 1:9.8, (43%)
X = PhSO N, R = Me, 5bd + 6bd, 1:7.8 (52%)
1a, X = TsN
1b, X = PhSO N
X = Ts, R = Me, 3aa (24%) + 4aa (35%)
X = PhSO N, R = Me, 3ba (21%) + 4ba (28%)
2
2
2
X = pMeO-PhSO N, R = Me, 5cd + 6cd, 1:10 (42%)
1c, X = pMeO-PhSO N
X = pMeO-PhSO N, R = Me, 3ca (33%) + 4ca (31%)
2
2
2
X = pCl-PhSO N, R = Me, 5dd + 6dd, 1:7.6 (46%)
1d, X = pCl-PhSO N
X = pCl-PhSO N, R = Me, 3da (43%) + 4da (19%)
2
2
2
X = pCF -PhSO N, R = Me, 5ed + 6ed, 1:8.5 (52%)
1e, X = pCF -PhSO N
X = pCF -PhSO N, R = Me, 3ea (36%) + 4ea (7%) + 5ea (6%)
3
2
3
2
3 2
X = pNO -PhSO N, R = Me, 5fd + 6fd, 1:5.9 (35%)*
1f, X = pNO -PhSO N
X = pNO -PhSO N, R = Me, 3fa (34%) + 4fa (5%) + 5fa (6%)
2 2
2
2
2
2
ꢀ
Schemeꢀ3.ꢀPt-catalysedꢀdivergentꢀalkoxy-ꢀandꢀhydroxycyclisationꢀofꢀpara-phenylsulfonylꢀtetheredꢀ1,5-bisallenes.ꢀ*ꢀ5-memberedꢀringꢀ18fꢀobtainedꢀinꢀ3%ꢀ(seeꢀSI).ꢀ
ꢀ
8 2
Figureꢀ1.ꢀꢀHammettꢀplotsꢀofꢀtheꢀhydroxycyclisationꢀproducts,ꢀcyclesꢀ5ꢀandꢀ6,ꢀinꢀTHF-d :D O,ꢀ5:1ꢀatꢀ50ºC.ꢀ
ꢀ
[
21]ꢀ
Figureꢀ2.ꢀHammettꢀplotsꢀofꢀtheꢀalkoxycyclisationꢀproducts,ꢀcycleꢀ4ꢀandꢀtrieneꢀ3,ꢀinTHF-d
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
8 3
:CD OD,ꢀ10:1.
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ3ꢀ
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Org aP nl ei ca s&e ꢀ Bd oi oꢀ nmo ot ꢀ lae dc j uu ls at rꢀ mC ahr eg imn si sꢀ try
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JournalꢀNameꢀ
ꢀCOMMUNICATIONꢀ
ꢀ
View Article Online
DOI: 10.1039/C7OB01469D
Inꢀorderꢀtoꢀprovideꢀalternativeꢀmechanismsꢀtoꢀexplainꢀtheꢀ
concaveꢀ Hammettꢀ plotsꢀ observed,ꢀ weꢀ exploredꢀ theꢀ
involvementꢀofꢀplatinumꢀhydridesꢀ(Pt-H)ꢀinꢀourꢀprocesses,ꢀ
whichꢀ haveꢀ beenꢀ reportedꢀ toꢀ formꢀ whenꢀ platinumꢀ
performedꢀ theꢀ reactionꢀ inꢀ theꢀ presenceꢀ ofꢀ TEMPO,ꢀ whichꢀ
hasꢀ beenꢀ reportedꢀ toꢀ inhibitꢀ theꢀ formationꢀ ofꢀ metalꢀ
[23]
hydrides, ꢀ andꢀ Et3SiH,ꢀ whichꢀ hasꢀ beenꢀ shownꢀ toꢀ formꢀ
Pt(IV)-HꢀbyꢀoxidativeꢀadditionꢀtoꢀPt(II)ꢀcomplexesꢀ(Schemeꢀ
[24]
4). ꢀꢀ
[22]ꢀ
complexesꢀ areꢀ inꢀ theꢀ presenceꢀ ofꢀ alcohols.
Weꢀ
TEMPO (20 mol%)
PtCl (MeCN) (5 mol%),
TEMPO (20 mol%)
•
PtCl (MeCN) (5 mol%),
2
2
2
2
AgSbF (10 mol%),
AgSbF (10 mol%),
6
6
OMe
+
X
OH
+ X
OH
OMe
X
X
HX
THF:CH OH (10:1)
THF:H O (1:3)
3
•
2
7
0˚C
70˚C
5
aa (43%) : 3aa (3%) - 23h
1a, X = NTs
1f, X = pNO PhSO N
5ad:6ad (37%, 1:5.2) - 20h
5fd:6fd (55%, 1:4.5) - 14h
5fa (10%) : 3fa (4%) - 30h, 54% conversion
2
2
Et SiH (20 mol%)
3
Et SiH (20 mol%)
3
•
PtCl (MeCN) (5 mol%),
PtCl (MeCN) (5 mol%),
2 2
2
2
AgSbF (10 mol%),
AgSbF (10 mol%),
6
OMe
+
6
OMe
TsN
No reaction
TsNH
TsN
THF:CH OH (10:1)
THF:H O (1:3)
3
2
•
7
0˚C
70˚C
4
aa (6%)
3aa (30%)
40 min
1a
ꢀ
3
Schemeꢀ4.ꢀReactionsꢀinꢀtheꢀpresenceꢀofꢀTEMPOꢀandꢀEt SiH.ꢀ
Theꢀreactionꢀofꢀbisallenesꢀ1aꢀ(Me-)ꢀandꢀ1fꢀ(NO2-)ꢀwithꢀMeOHꢀinꢀ stepꢀ formingꢀ theꢀ Pt(II)-π-allylꢀ cation;ꢀ KIEꢀ ~ꢀ 1;ꢀ methanolꢀ notꢀ
theꢀ presenceꢀ ofꢀ TEMPOꢀ ledꢀ toꢀ anꢀ increaseꢀ inꢀ reactionꢀ time,ꢀ involved),ꢀ followedꢀ byꢀ nucleophilicꢀ attackꢀ toꢀ theꢀ π-allyl-Pt(II)ꢀ
withꢀ formationꢀ ofꢀ trienesꢀ 3ꢀ andꢀ theꢀ azepineꢀ cycleꢀ 5ꢀ (notꢀ intermediateꢀ9ꢀtoꢀgiveꢀ4ꢀandꢀPt(0).ꢀ
observedꢀ beforeꢀ underꢀ theseꢀ conditions),ꢀ inhibitingꢀ theꢀ Pt(II)-Hꢀcanꢀalsoꢀbeꢀinvolvedꢀinꢀtheꢀformationꢀofꢀtrienesꢀfromꢀ
formationꢀ ofꢀ vinylcyclohexenesꢀ 4ꢀ (Schemeꢀ 4).ꢀ Inꢀ contrast,ꢀ bisallenesꢀ bearingꢀ ED-substituentꢀ inꢀ theꢀ sulfonamide.ꢀ
reactionꢀofꢀbisallenesꢀ1aꢀandꢀ1fꢀwithꢀH2Oꢀinꢀtheꢀpresenceꢀofꢀ Cyclisationꢀ ofꢀ intermediateꢀ 10ꢀ withꢀ semiconcertedꢀ attackꢀ ofꢀ
TEMPOꢀledꢀtoꢀhydro-1H-azepinesꢀ5ꢀandꢀ6ꢀsimilarlyꢀtoꢀwhenꢀnoꢀ theꢀmethanolꢀtoꢀgiveꢀplatinacycleꢀ11ꢀ(ρꢀ=ꢀ-0.9,ꢀslightꢀdecreaseꢀ
TEMPOꢀ wasꢀ present.ꢀ Besides,ꢀ Et3SiHꢀ inhibitedꢀ theꢀ reactionꢀ inꢀelectronꢀdensityꢀinꢀtheꢀPt(II)-π-allylꢀwithꢀcationicꢀcharacterꢀ
withꢀH2Oꢀandꢀledꢀtoꢀtheꢀfastꢀformationꢀofꢀtrieneꢀ3aaꢀandꢀcycleꢀ beforeꢀ nucleophilicꢀ attack;ꢀ primaryꢀ KIEꢀ ~ꢀ 1.8ꢀ inꢀ methanol;ꢀ
4
aaꢀwithꢀMeOH,ꢀalthoughꢀinꢀdifferentꢀyieldꢀthanꢀtheꢀstandardꢀ inverseꢀsecondaryꢀKIE,ꢀchangeꢀinꢀhybridizationꢀinꢀtheꢀterminalꢀ
2
3
reactionꢀ (Schemeꢀ 5).ꢀ Thisꢀ suggestsꢀ thatꢀ Pt(II)-Hꢀ couldꢀ beꢀ carbonꢀfromꢀsp ꢀtoꢀsp ),ꢀfollowedꢀbyꢀfastꢀ1,5-Hꢀshiftꢀtoꢀgiveꢀ12ꢀ
indeedꢀ involvedꢀ asꢀ activeꢀ catalystsꢀ inꢀ theꢀ formationꢀ ofꢀ vinyl- andꢀreductiveꢀeliminationꢀwouldꢀgiveꢀtrienesꢀ3.ꢀAlternatively,ꢀ
tetrahydropyridinesꢀ 4ꢀ andꢀ trienesꢀ 3ꢀ inꢀ theꢀ reactionꢀ withꢀ trienesꢀ withꢀ EW-substituentsꢀ inꢀ theꢀ sulfonamideꢀ couldꢀ beꢀ
MeOH,ꢀbutꢀformationꢀofꢀcycloheptadienesꢀ5ꢀandꢀ6ꢀwithꢀwaterꢀ formedꢀfromꢀ13ꢀviaꢀnucleophilicꢀattackꢀ(ρꢀ=ꢀ0.6,ꢀslightꢀincreaseꢀ
[
25]
occursꢀwithꢀnoꢀinvolvementꢀofꢀPt-Hꢀasꢀactiveꢀcatalyst. ꢀꢀ
Inꢀ viewꢀ ofꢀ theseꢀ results,ꢀ weꢀ proposeꢀ differentꢀ mechanismsꢀ giveꢀ intermediatesꢀ 16ꢀ orꢀ 17,ꢀ whichꢀ wouldꢀ sufferꢀ elimination,ꢀ
inꢀelectronꢀdensity)ꢀandꢀcyclisationꢀofꢀtheꢀvinyl-platinumꢀ14ꢀtoꢀ
[28]ꢀ
dependingꢀonꢀtheꢀnucleophileꢀandꢀtheꢀelectronicꢀpropertiesꢀofꢀ aidedꢀ byꢀ theꢀ EWꢀ propertiesꢀ ofꢀ theꢀ sulfonamideꢀ group,
ꢀ
theꢀ tetherꢀ inꢀ bisallenesꢀ 1ꢀ forꢀ theꢀ formationꢀ ofꢀ 6-ꢀ andꢀ 7- withoutꢀ theꢀ involvementꢀ ofꢀ Pt(II)-H. Thisꢀ alternativeꢀ pathwayꢀ
memberedꢀringsꢀandꢀtrienesꢀ(Schemeꢀ5).ꢀ seemsꢀtoꢀbeꢀoperativeꢀforꢀtheꢀformationꢀofꢀazepinesꢀ5ꢀinꢀtheꢀ
ꢀ
InꢀtheꢀreactionꢀwithꢀMeOH,ꢀformationꢀofꢀPt(II)-Hꢀwouldꢀexplainꢀ reactionꢀwithꢀmethanolꢀinꢀtheꢀpresenceꢀofꢀTEMPOꢀandꢀatꢀhighꢀ
theꢀinductionꢀperiodꢀobservedꢀandꢀtheꢀorderꢀ1ꢀinꢀMeOHꢀandꢀPtꢀ MeOHꢀconcentration.ꢀ
[26]
(
theꢀ internalꢀ orꢀ externalꢀ doubleꢀ bondsꢀ ofꢀ oneꢀ ofꢀ theꢀ allenesꢀ activeꢀ catalystꢀ inꢀ theꢀ formationꢀ ofꢀ azepinesꢀ inꢀ water.ꢀ Theꢀ
“offꢀ cycle”,ꢀ rate-limitingꢀ step). ꢀ Additionꢀ ofꢀ theꢀ Pt(II)-Hꢀ toꢀ TheꢀtrappingꢀexperimentsꢀalsoꢀshowedꢀthatꢀPt-Hꢀareꢀnotꢀtheꢀ
[27]
wouldꢀ giveꢀ intermediatesꢀ 7ꢀ andꢀ 10. ꢀ Formationꢀ ofꢀ cycleꢀ 4ꢀ reactionꢀinꢀwaterꢀwouldꢀproceedꢀthroughꢀcoordinationꢀofꢀtheꢀ
[29]
whenꢀEW-substituentsꢀareꢀpresentꢀinꢀtheꢀsulfonamideꢀcouldꢀbeꢀ platinumꢀ toꢀ one ꢀ orꢀ bothꢀ allenes,ꢀ 13,ꢀ followedꢀ byꢀ
explainedꢀ byꢀ nucleophilicꢀ additionꢀ toꢀ 7ꢀ withꢀ concomitantꢀ nucleophilicꢀ attackꢀ andꢀ carbocyclisationꢀ viaꢀ aꢀ vinyl-Pt(II)ꢀ
formationꢀofꢀplatinacycleꢀ8ꢀ(ρꢀ=ꢀ0.9,ꢀslightꢀincreaseꢀinꢀelectronꢀ intermediateꢀ14ꢀwithꢀEW-substitutedꢀsulfonamidesꢀ(ρꢀ=ꢀ0.7ꢀforꢀ
[
11b,30]ꢀ
densityꢀinꢀaꢀconcertedꢀprocessꢀasꢀtheꢀturnover-limitingꢀstep),ꢀ cycleꢀ 5ꢀ andꢀ 0.4ꢀ forꢀ cycleꢀ 6)
fromꢀwhichꢀreductiveꢀeliminationꢀwouldꢀformꢀcycleꢀ4ꢀandꢀPt(0),ꢀ platina(IV)cycleꢀ15ꢀ(ED-substituents,ꢀρꢀ=ꢀ-1.5ꢀforꢀcycleꢀ5ꢀandꢀ-
orꢀ formationꢀ ofꢀ
ꢀ
[5b,31]ꢀ
thatꢀcanꢀbeꢀprotonatedꢀbyꢀMeOHꢀtoꢀregenerateꢀPt-H.
2.0ꢀforꢀcycleꢀ6),
followedꢀbyꢀnucleophilicꢀattackꢀtoꢀformꢀ16ꢀ
Alternatively,ꢀtheꢀreactionꢀofꢀbisallenesꢀwithꢀED-substituentsꢀinꢀ orꢀ17.ꢀWeꢀdidꢀnotꢀobserveꢀisomerisationꢀofꢀcyclesꢀ5ꢀandꢀ6ꢀonceꢀ
theꢀsulfonamideꢀwouldꢀfavourꢀcarbometalationꢀofꢀ7ꢀ(ρꢀ=ꢀ-2.9,ꢀ formedꢀorꢀdeuteriumꢀscramblingꢀinꢀanyꢀofꢀtheꢀallylicꢀpositionꢀ
moderateꢀdecreaseꢀinꢀelectronꢀdensityꢀinꢀtheꢀturnover-limitingꢀ whenꢀtheꢀreactionꢀwasꢀcarriedꢀoutꢀinꢀdeuteratedꢀwater.ꢀThisꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
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Page 5 of 8
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JournalꢀNameꢀ
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suggestsꢀ thatꢀ equilibriumꢀ betweenꢀ theꢀ Pt(II)-π-allylꢀ Inꢀconclusion,ꢀunprecedentedꢀplatinum-catalysedꢀhydroxy-ꢀanlndꢀ
View Article O ine
intermediatesꢀ16ꢀandꢀ17ꢀcouldꢀbeꢀresponsibleꢀforꢀtheꢀfavouredꢀ alkoxycyclisationsꢀofꢀbisallenesꢀtoꢀgiveꢀ6 D- ꢀ Oo rI :ꢀ 17 0- .m1 0 e3 m9 / Cb 7e Or eB d0 1ꢀ r4 i6n 9 gD sꢀ
generationꢀ ofꢀ cycleꢀ 6.ꢀ Theꢀ analysisꢀ ofꢀ Hammettꢀ constantsꢀ vsꢀ withꢀ extraꢀ functionalitiesꢀ haveꢀ beenꢀ discovered.ꢀ Theseꢀ newꢀ
log(ratioꢀ 6:5)ꢀ wasꢀ linearꢀ withꢀ aꢀ slightꢀ negativeꢀ slopeꢀ (ρꢀ =ꢀ - reactionsꢀ areꢀ importantꢀ additionsꢀ toꢀ theꢀ growingꢀ palletꢀ ofꢀ
[
32]
0
.17), ꢀwhichꢀindicatesꢀthatꢀtheꢀequilibriumꢀcouldꢀbeꢀslightlyꢀ bisalleneꢀ chemistryꢀ andꢀ highlightꢀ theꢀ importanceꢀ ofꢀ theꢀ lessꢀ
favouredꢀ towardꢀ intermediateꢀ 17ꢀ withꢀ ED-substitutedꢀ exploredꢀ platinumꢀ catalysisꢀ inꢀ thisꢀ area.ꢀ Althoughꢀ simpleꢀ atꢀ
sulfonamidesꢀ andꢀ towardꢀ 16ꢀ withꢀ EW-substitutedꢀ ones.ꢀ firstꢀ sight,ꢀ aꢀ deeperꢀ mechanisticꢀ investigationꢀ revealedꢀ aꢀ
Besides,ꢀintramolecularꢀprotodemetallationꢀofꢀintermediateꢀ16ꢀ complexꢀ scenarioꢀ withꢀ severalꢀ pathwaysꢀ involvedꢀ dependingꢀ
isꢀpossibleꢀtoꢀformꢀcycleꢀ5,ꢀwhereasꢀinꢀtheꢀcaseꢀofꢀcycleꢀ6,ꢀthisꢀ onꢀ nucleophileꢀ andꢀ electronicꢀ propertiesꢀ ofꢀ theꢀ bisallene.ꢀ
protonꢀtransferꢀinꢀintermediateꢀ17ꢀisꢀmoreꢀdifficultꢀandꢀhasꢀtoꢀ Understandingꢀ theseꢀ mechanismsꢀ withꢀ helpꢀ toꢀ improveꢀ
beꢀassistedꢀbyꢀanꢀexternalꢀmoleculeꢀofꢀH2O.ꢀThisꢀisꢀsupportedꢀ efficiencyꢀ andꢀ extendꢀ thisꢀ methodologyꢀ toꢀ moreꢀ complexꢀ
byꢀtheꢀincreaseꢀinꢀcycleꢀ6ꢀformationꢀasꢀtheꢀamountꢀofꢀH2Oꢀinꢀ systemsꢀ withꢀ interestꢀ forꢀ syntheticꢀ chemistsꢀ andꢀ
[
33,34]
theꢀ mediaꢀ increasesꢀ inꢀ aꢀ linearꢀ correlationꢀ forꢀ theꢀ TsN- pharmaceuticalꢀindustry.
ꢀ
ꢀ
derivativeꢀ(seeꢀSI).ꢀꢀ
ꢀ
ꢀ
•
•
t.l.s.
R = alkyl,
X = ED
H
H
H
X
X
[Pt(II)]
H
-
H+
X
[Pt(II)]
•
7 •
-H+
H
X
[
Pt(II)]
t.l.s.
R = alkyl,
X = ED
1
[Pt(II)]
HOR
X
t.l.s.
1,5-H shift
R = alkyl,
X = EW
HOR
9
1
0
1
1
OR
[Pt(II)]
X
HOR
OR
[
Pt(II)-H]
8
-
H+
[
Pt(II)]
r.l.s.
R = alkyl
HX
H
H
ROH
Red. El.
1
2 OR
ROH
H
X
X
OH
OH
[
Pt(0)]
Red. El.
[Pt(0)]
X
5
6
[
Pt(II)]
-
OR
4
H2O
H2O
1
R = H
•
[
Pt(II)]
[Pt(II)]
t.l.s.
OR
R = H
X = ED
X
[Pt(II)]
H+
-H+
X
[Pt(IV)]
ROH
X
X
OR
OR
•
3
13
HX
1
5
1
7
16
ROH
•
-
H+
t.l.s.
X
[Pt(II)]
R = alkyl, H
X = EW
1
4
OR
Schemeꢀ5.ꢀProposedꢀdivergentꢀmechanisticꢀpathways.ꢀActiveꢀspeciesꢀ[Pt(II)] ꢀandꢀ[Pt(II)-H]ꢀareꢀpresentedꢀforꢀsimplicity.ꢀr.l.s.ꢀ=ꢀrateꢀlimitingꢀstep.ꢀt.l.s.ꢀ=ꢀturnover-limitingꢀstep.ꢀ
ꢀ
+
R.ꢀZimmer,ꢀC.ꢀU.ꢀDinesh,ꢀE.ꢀNandananꢀandꢀF.ꢀA.ꢀKhan,ꢀ
Chem.ꢀ Rev.,ꢀ 2000,ꢀ 100,ꢀ 3067;ꢀ h)ꢀ A.ꢀ S.ꢀ K.ꢀ Hashmi,ꢀ
Angew.ꢀChem.ꢀInt.ꢀEd.ꢀEngl.,ꢀ2000,ꢀ39,ꢀ3590.ꢀ
Forꢀreviewsꢀonꢀtheꢀchemistryꢀofꢀconjugatedꢀbisallenes,ꢀ
see:ꢀa)ꢀR.ꢀStammꢀandꢀH.ꢀHopf,ꢀBelsteinꢀJ.ꢀOrg.ꢀChem.,ꢀ
2013,ꢀ9,ꢀ36;ꢀb)ꢀH.ꢀHopfꢀandꢀG.ꢀMarkopolus,ꢀBelsteinꢀJ.ꢀ
Org.ꢀChem.,ꢀ2012,ꢀ8,ꢀ1936.ꢀ
Forꢀ reviewsꢀ onꢀ theꢀ chemistryꢀ ofꢀ non-conjugatedꢀ
bisallenes,ꢀ see:ꢀ a)ꢀ B.ꢀ Alcaide,ꢀ P.ꢀ Almendrosꢀ andꢀ C.ꢀ
Aragoncillo,ꢀ Chem.ꢀ Soc.ꢀ Rev.,ꢀ 2014,ꢀ 43,ꢀ 3106;ꢀ b)ꢀ G.ꢀ
Chen,ꢀX.ꢀJiang,ꢀC.ꢀFuꢀandꢀS.ꢀMa,ꢀChem.ꢀLett.,ꢀ2010,ꢀ39,ꢀ
78.ꢀ
Notesꢀandꢀreferencesꢀ
1
Forꢀselectedꢀreviews,ꢀsee: a)ꢀThemedꢀissue:ꢀProgressꢀinꢀ
2
3
alleneꢀ chemistryꢀ (guestꢀ editorsꢀ B.ꢀ Alcaideꢀ andꢀ P.ꢀ
Almendros),ꢀChem.ꢀSoc.ꢀRev.ꢀ2014,ꢀ43,ꢀ2879;ꢀb)ꢀS.ꢀYuꢀ
andꢀS.ꢀMa,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2012,ꢀ51,ꢀ3074;ꢀc)ꢀM.ꢀ
Lópezꢀ andꢀ J.ꢀ L.ꢀ Mascareñas,ꢀ Chem.ꢀ Eur.ꢀ J.,ꢀ 2011,ꢀ 17,ꢀ
418;ꢀ d)ꢀ C.ꢀ Aubert,ꢀ L.ꢀ Fensterbank,ꢀ P.ꢀ Garcia,ꢀ M.ꢀ
Malacriaꢀ andꢀ A.ꢀ Simonneau,ꢀ Chem.ꢀ Rev.,ꢀ 2011,ꢀ 111,ꢀ
1
1
954;ꢀ e)ꢀ N.ꢀ Krauseꢀ andꢀ C.ꢀ Winter,ꢀ Chem.ꢀ Rev.,ꢀ 2011,ꢀ
11,ꢀ 1994;ꢀ f)ꢀ B.ꢀ Alcaide,ꢀ P.ꢀ Almendrosꢀ andꢀ M.ꢀ T.ꢀ
MartínezꢀdelꢀCampo,ꢀChem.ꢀEur.ꢀJ.,ꢀ2010,ꢀ16,ꢀ5836;ꢀg)ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ5ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Org aP nl ei ca s&e ꢀ Bd oi oꢀ nmo ot ꢀ lae dc j uu ls at rꢀ mC ahr eg imn si sꢀ try
Page 6 of 8
JournalꢀNameꢀ
ꢀCOMMUNICATIONꢀ
4
a)ꢀX.ꢀJiang,ꢀX.ꢀChengꢀandꢀS.ꢀMa,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ
006,ꢀ45,ꢀ8009;ꢀb)ꢀY.-T.ꢀHong,ꢀS.-K.ꢀYoon,ꢀS.-K.ꢀKangꢀandꢀ
A.ꢀHoffmann-RoderꢀandꢀN.ꢀKrause,ꢀOrg.ꢀLVeietwt.A,ꢀrt2ic0le0O1n,lꢀin3e,ꢀ
2537.ꢀ
2
DOI: 10.1039/C7OB01469D
C.-MoꢀYu,ꢀEur.ꢀJ.ꢀOrg.ꢀChem.,ꢀ2004,ꢀ4628;ꢀc)ꢀS.-K.ꢀKang,ꢀ
T.-G.ꢀBaik,ꢀA.ꢀN.ꢀKulak,ꢀY.-H.ꢀHa,ꢀY.ꢀLimꢀandꢀJ.ꢀPark,ꢀJ.ꢀ
Am.ꢀChem.ꢀSoc.,ꢀ2000,ꢀ122,ꢀ11529.ꢀ
a)ꢀL.ꢀPingꢀandꢀS.ꢀMa,ꢀChin.ꢀJ.ꢀChem.,ꢀ2010,ꢀ28,ꢀ1600P;ꢀb).ꢀ
LiuꢀandꢀS.ꢀMa,ꢀOrg.ꢀLett.,ꢀ2007,ꢀ9,ꢀ2095.ꢀForꢀexamplesꢀ
ofꢀ [2+2+1]-cycloadditionꢀ formingꢀ 7-memberedꢀ rings,ꢀ
see:ꢀc)ꢀT.ꢀKawamura,ꢀF.ꢀInagaki,ꢀS.ꢀNarita,ꢀY.ꢀTakahashi,ꢀ
S.ꢀHirata,ꢀS.ꢀKitagakuꢀandꢀC.ꢀMukai,ꢀChem.ꢀEur.ꢀJ.,ꢀ2010,ꢀ
16 Y.ꢀHorino,ꢀM.ꢀR.ꢀLuzungꢀandꢀF.ꢀD.ꢀToste,ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.,ꢀ2006,ꢀ128,ꢀ11364.ꢀꢀ
17 J.ꢀBures,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2016,ꢀ55,ꢀ2028.ꢀ
18 Dimericꢀ cationicꢀ hydroxy-platinumꢀ complexesꢀ haveꢀ
beenꢀproposedꢀbefore,ꢀsee:ꢀG.ꢀW.ꢀBushnell,ꢀK.ꢀR.ꢀDixon,ꢀ
R.ꢀG.ꢀHunterꢀandꢀJ.ꢀJ.ꢀMcFarland,ꢀCan.ꢀJ.ꢀChem.,ꢀ1972,ꢀ
50,ꢀ3694.ꢀAnꢀout-of-cycleꢀequilibriumꢀbetweenꢀcationicꢀ
platinumꢀcomplexes,ꢀactiveꢀspeciesꢀinꢀtheꢀreaction,ꢀandꢀ
hydroxyꢀ dimersꢀ couldꢀ explainꢀ theꢀ inductionꢀ periodꢀ
5
1
6,ꢀ 5173;ꢀ J;ꢀ d)ꢀ F.ꢀ Inagaki,ꢀ S.ꢀ Narita,ꢀ T.ꢀ Hasegawa,ꢀ S.ꢀ
KitagakiꢀandꢀC.ꢀMukai,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2009,ꢀ48,ꢀ
007ꢀ(oneꢀexampleꢀofꢀaꢀ6-memberedꢀringꢀreported);ꢀe)ꢀ
2
observedꢀ inꢀ water.ꢀ Thisꢀ isꢀ lessꢀ likelyꢀ toꢀ occurꢀ inꢀ D O,ꢀ
explainingꢀ theꢀ shorterꢀ inductionꢀ periodꢀ observedꢀ inꢀ
deuteratedꢀwater.ꢀ
2
H.ꢀPark,ꢀE.ꢀKim,ꢀH.-M.ꢀKim,ꢀS.ꢀY.ꢀChoiꢀandꢀY.ꢀK.ꢀChung,ꢀ
Chem.ꢀCommun.,ꢀ2008,ꢀ2388.ꢀ
H
O
2+
-
[SbF6 ]2 + 2 HSbF6
6
a)ꢀS.ꢀMaꢀandꢀL.ꢀLu,ꢀChem.ꢀAsianꢀJ.,ꢀ2007,ꢀ2,ꢀ199;ꢀb)ꢀS.ꢀ
Ma,ꢀP.ꢀLu,ꢀL.ꢀLu,ꢀH.ꢀHou,ꢀJ.ꢀWei,ꢀQ.ꢀHe,ꢀZ.ꢀGu,ꢀX.ꢀJiangꢀ
andꢀX.ꢀJin,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2005,ꢀ44,ꢀ5275.ꢀꢀ
S.ꢀM.ꢀKim,ꢀJ.ꢀH.ꢀPark,ꢀY.ꢀK.ꢀKangꢀandꢀY.ꢀK.ꢀChung,ꢀAngew.ꢀ
Chem.ꢀInt.ꢀEd.,ꢀ2009,ꢀ48,ꢀ4532.ꢀ
a)ꢀ C.ꢀ Hurtado-Rodrigo,ꢀ S.ꢀ Hoehneꢀ andꢀ M.ꢀ P.ꢀ Muñoz,ꢀ
Chem.ꢀCommun.,ꢀ2014,ꢀ50,ꢀ1494;ꢀb)ꢀM.ꢀP.ꢀMuñoz,ꢀM.ꢀC.ꢀ
deꢀlaꢀTorreꢀandꢀM.ꢀA.ꢀSierra,ꢀ Chem.ꢀEur.ꢀJ.,ꢀ2012,ꢀ18,ꢀ
2
2 H O
2
[(CH
3
CN)
2
Pt]2+ [SbF
6
-]
2
(CH CN) Pt
3
Pt(CH CN)2
3
2
O
H
ꢀ
7
8
1
2
9
0
M.ꢀGómez-GallegoꢀandꢀM.ꢀA.ꢀSierra,ꢀChem.ꢀRev.,ꢀ2011,ꢀ
11,ꢀ4857.ꢀ
a)ꢀJ.ꢀO.ꢀSchreck,ꢀJ.ꢀChem.ꢀEd.,ꢀ1971,ꢀ48,ꢀ103;ꢀb)ꢀH.ꢀH.ꢀ
Jaffé,ꢀ Chem.ꢀ Rev.,ꢀ 1953,ꢀ 53,ꢀ 191;ꢀ c)ꢀ L.ꢀ P.ꢀ Hammett,ꢀ J.ꢀ
Am.ꢀChem.ꢀSoc.,ꢀ1937,ꢀ59,ꢀ96.ꢀ
1
4
499;ꢀ c)ꢀ M.ꢀ P.ꢀ Muñoz,ꢀ M.ꢀ C.ꢀ deꢀ laꢀ Torreꢀ andꢀ M.ꢀ A.ꢀ
2
2
2
1
2
3
Cyclesꢀ 4eaꢀ andꢀ 4faꢀ wereꢀ obtainedꢀ inꢀ <ꢀ 5%ꢀ inꢀ theꢀ
reactionsꢀatꢀ50ꢀ C,ꢀthereforeꢀaccurateꢀkineticꢀdataꢀforꢀ
thoseꢀcompoundsꢀcouldꢀnotꢀbeꢀobtainedꢀandꢀhasꢀnotꢀ
beenꢀincludedꢀinꢀtheꢀHammettꢀplot.ꢀ
a)ꢀ A.ꢀ N.ꢀ Campbellꢀ andꢀ M.ꢀ R.ꢀ Gagné,ꢀ Organometallics,ꢀ
Sierra,ꢀAdv.ꢀSynth.ꢀCatal.,ꢀ2010,ꢀ352,ꢀ2189.ꢀReviews:ꢀd)ꢀ
M.ꢀP.ꢀMuñoz,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2014,ꢀ43,ꢀ3164;ꢀe)ꢀM.ꢀP.ꢀ
Muñoz,ꢀOrg.ꢀBiomol.ꢀChem.,ꢀ2012,ꢀ10,ꢀ3584.ꢀꢀ
J.ꢀCheng,ꢀX.ꢀJiangꢀandꢀS.ꢀMa,ꢀOrg.ꢀLett.,ꢀ2011,ꢀ13,ꢀ5200.ꢀꢀ
Forꢀ anꢀ exampleꢀ ofꢀ 7-memberedꢀ bicyclicꢀ structuresꢀ
obtainedꢀbyꢀintramolecularꢀattackꢀofꢀanꢀalcoholꢀtoꢀtheꢀ
centralꢀcarbonꢀofꢀoneꢀofꢀtheꢀallenesꢀinꢀaꢀ1,ω-bisallenolꢀ
system,ꢀsee:ꢀY.ꢀDeng,ꢀY.ꢀShiꢀandꢀS.ꢀMa,ꢀOrg.ꢀLett.,ꢀ2009,ꢀ
o
9
1
0
1
2
007,ꢀ 26,ꢀ 2788;ꢀ b)ꢀ H.ꢀ E.ꢀ Bryndza,ꢀ J.ꢀ C.ꢀ Calabrese,ꢀ M.ꢀ
Marsi,ꢀD.ꢀC.ꢀRoe,ꢀW.ꢀTamꢀandꢀJ.ꢀE.ꢀBercaw,ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.,ꢀ1986,ꢀ108,ꢀ4805.ꢀ
A.ꢀ C.ꢀ Albéniz,ꢀ P.ꢀ Espinet,ꢀ R.ꢀ López-Férnandezꢀ andꢀ A.ꢀ
Sen,ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.,ꢀ 2002,ꢀ 124,ꢀ 11278.ꢀ Radicalꢀ
mechanismsꢀ cannotꢀ beꢀ completelyꢀ ruledꢀ out:ꢀ H.ꢀ C.ꢀ
Clarkꢀ andꢀ C.ꢀ S.ꢀ Wong,ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.,ꢀ 1977,ꢀ 99,ꢀ
1
1,ꢀ1205.ꢀForꢀreactionꢀwithꢀ1,5-bis(1,2-allenylketones)ꢀ
see:ꢀY.ꢀDeng,ꢀC.ꢀFuꢀandꢀS.ꢀMa,ꢀChem.ꢀEur.ꢀJ.,ꢀ2011,ꢀ17,ꢀ
976.ꢀꢀ
4
1
a)ꢀY.ꢀN.ꢀLim,ꢀH.-T.ꢀKim,ꢀH.-S.ꢀYoonꢀandꢀH.-Y.ꢀJang,ꢀBull.ꢀ
KoreanꢀChem.ꢀSoc.,ꢀ2011,ꢀ32,ꢀ3117.ꢀb)ꢀForꢀPt-catalysedꢀ
hydrativeꢀ cyclisationꢀ ofꢀ allenynes,ꢀ see:ꢀ T.ꢀ Matsuda,ꢀ S.ꢀ
Kadowakiꢀ andꢀ M.ꢀ Murakami,ꢀ Helv.ꢀ Chim.ꢀ Acta,ꢀ 2006,ꢀ
7
073.ꢀ
2
2
4
5
a)ꢀD.ꢀH.ꢀNguyen,ꢀY.ꢀCoppel,ꢀM.ꢀUrrutigoityꢀandꢀP.ꢀKalck,ꢀ
J.ꢀOrganomet.ꢀChem.,ꢀ2005,ꢀ690,ꢀ2947;ꢀb)ꢀD.ꢀChan,ꢀS.ꢀB.ꢀ
Duckett,ꢀS.ꢀL.ꢀHeath,ꢀI.ꢀG.ꢀKhazal,ꢀR.ꢀN.ꢀPerutz,ꢀS.ꢀSabo-
EtienneꢀandꢀP.ꢀL.ꢀTimmins,ꢀOrganometallics,ꢀ2004,ꢀ23,ꢀ
8
9,ꢀ1672.ꢀ
1
1
2
3
Forꢀformationꢀofꢀtetraenesꢀfromꢀcupracyclopenteneꢀinꢀ
aꢀ reactionꢀ ofꢀ bisallenes,ꢀ see:ꢀ S.ꢀ Kitagaki,ꢀ M.ꢀ Kajita,ꢀ S.ꢀ
NaritaꢀandꢀC.ꢀMukai,ꢀOrg.ꢀLett.,ꢀ2012,ꢀ14,ꢀ1366.ꢀ
5
744.ꢀ
AlthoughꢀPt(IV)-Hꢀwouldꢀbeꢀformedꢀinꢀtheꢀreactionꢀwithꢀ
Et SiH,ꢀ weꢀ proposeꢀ thatꢀ inꢀ theꢀ standardꢀ reaction,ꢀ
Pt(II)-H]ꢀ areꢀ theꢀ activeꢀ speciesꢀ inꢀ theꢀ catalyticꢀ cycle.ꢀ
3
Forꢀ anꢀ exampleꢀ ofꢀ formationꢀ ofꢀ simpleꢀ
vinylcyclohexenesꢀ
[
viaꢀ
gold-catalysedꢀ
Theseꢀ areꢀ formedꢀ initiallyꢀ byꢀ β-hydrideꢀ eliminationꢀ inꢀ
platinum(II)-alkoxidesꢀ complexesꢀ (seeꢀ Refꢀ 21)ꢀ andꢀ areꢀ
alsoꢀ regeneratedꢀ byꢀ protonationꢀ ofꢀ Pt(0)ꢀ speciesꢀ
generatedꢀafterꢀtheꢀfirstꢀturnoverꢀcycle.ꢀꢀ
cycloisomerisationꢀofꢀenallenes,ꢀsee:ꢀM.ꢀA.ꢀTarselli,ꢀA.ꢀ
R.ꢀChianese,ꢀS.ꢀJ.ꢀLeeꢀandꢀM.ꢀRꢀGagné,ꢀAngew.ꢀChem.ꢀ
Int.ꢀEd.,ꢀ2007,ꢀ46,ꢀ6670.ꢀ
Forꢀ Pt-catalysedꢀ hydroxy-ꢀ andꢀ alkoxycyclisationꢀ ofꢀ
enynesꢀsee:ꢀa)ꢀM.ꢀMéndez,ꢀM.ꢀP.ꢀMuñoz,ꢀC.ꢀNevado,ꢀD.ꢀ
J.ꢀCárdenasꢀandꢀA.ꢀM.ꢀEchavarren,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ
1
1
4
5
2
6
Complexꢀ equilibriumꢀ betweenꢀ cationicꢀ platinum(II)ꢀ
complexes,ꢀ
hydridesꢀandꢀdi-hydridesꢀmightꢀbeꢀinvolved.ꢀFormationꢀ
ofꢀ [Pt(II)-(H) ]ꢀ speciesꢀ willꢀ beꢀ moreꢀ difficultꢀ withꢀ
platinum(II)-alkoxides,ꢀ
platinum(II)-
2
001,ꢀ123,ꢀ10511;ꢀb)ꢀM.ꢀMéndez,ꢀM.ꢀP.ꢀMuñozꢀandꢀA.ꢀ
2
M.ꢀEchavarren,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2000,ꢀ122,ꢀ11549.ꢀ
Noꢀ reactionꢀ orꢀ complexꢀ mixturesꢀ wereꢀ obtainedꢀ withꢀ
otherꢀ metalsꢀ (seeꢀ SI).ꢀ Goldꢀ complexesꢀ gaveꢀ methanolꢀ
additionꢀ ontoꢀ eachꢀ alleneꢀ followingꢀ reportedꢀ
selectivity,ꢀ butꢀ noꢀ cyclisationꢀ wasꢀ observed.ꢀ Forꢀ
selectedꢀexamples,ꢀsee:ꢀa)ꢀM.ꢀS.ꢀHadfieldꢀandꢀA.-L.ꢀLee,ꢀ
Org.ꢀLett.,ꢀ2010,ꢀ12,ꢀ484;ꢀb)ꢀR.ꢀS.ꢀPatonꢀandꢀF.ꢀMaseras,ꢀ
Org.ꢀLett.,ꢀ2009,ꢀ11,ꢀ2237;ꢀc)ꢀD.-M.ꢀCui,ꢀZ.-L.ꢀZhengꢀandꢀ
C.ꢀZhang,ꢀJ.ꢀOrg.ꢀChem.,ꢀ2009,ꢀ74,ꢀ1426;ꢀd)ꢀZ.ꢀZhang,ꢀS.ꢀ
Du,ꢀ A.ꢀ S.ꢀ Fisherꢀ andꢀ R.ꢀ A.ꢀ Widenhoefer,ꢀ Tetrahedron,ꢀ
deuteratedꢀmethanol,ꢀexplainingꢀtheꢀshorterꢀinductionꢀ
period.ꢀ
[
(CH3CN)2PtCl2]
AgSbF6
AgSbF6
AgSbF6
[(CH CN) PtCl]+ [SbF6-]
[(CH3CN)2Pt]2+ [SbF6-]2
CH3OH
3
2
CH3OH
[
(CH3CN)2Pt(OCH3)Cl]
[(CH3CN)2Pt-OCH3]+ [SbF6-]2
2
009,ꢀ 65,ꢀ 1794;ꢀ e)ꢀ N.ꢀ Nishinaꢀ andꢀ Y.ꢀ Yamamoto,ꢀ
AgSbF6
[(CH3CN)2Pt-H]+ [SbF6-]2
[(CH3CN)2Pt(OCH3)2]
Tetrahedron,ꢀ2009,ꢀ65,ꢀ1799;ꢀf)ꢀD.-M.ꢀCui,ꢀK.ꢀR.ꢀYuꢀandꢀ
C.ꢀ Zhang,ꢀ Synlett,ꢀ 2009,ꢀ 1103;ꢀ g)ꢀ Z.ꢀ Zhangꢀ andꢀ R.ꢀ A.ꢀ
Widenhoefer,ꢀOrg.ꢀLett.,ꢀ2008,ꢀ10,ꢀ2079;ꢀh)ꢀN.ꢀNishinaꢀ
andꢀYamamoto,ꢀY.ꢀTetrahedronꢀLett.,ꢀ2008,ꢀ49,ꢀ4908;ꢀi)ꢀ
[(CH3CN)2Pt-H(Cl)]
[(CH3CN)2Pt(H)2]
[(CH CN) Pt-H(OCH )]
3
2
3
ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ6ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 7 of 8
Org aP nl ei ca s&e ꢀ Bd oi oꢀ nmo ot ꢀ lae dc j uu ls at rꢀ mC ahr eg imn si sꢀ try
JournalꢀNameꢀ
ꢀCOMMUNICATIONꢀ
2
2
2
3
3
3
3
7
8
9
0
1
2
3
H.-T.ꢀKim,ꢀH.-S.ꢀYoon,ꢀW.-Y.ꢀJang,ꢀY.ꢀK.ꢀKangꢀandꢀH.-Y.ꢀ
Jang.,ꢀEur.ꢀJ.ꢀOrg.ꢀChem.,ꢀ2011,ꢀ3748.ꢀ
View Article Online
DOI: 10.1039/C7OB01469D
C.ꢀFerrerꢀandꢀA.ꢀM.ꢀEchavaren,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ
2
006,ꢀ45,ꢀ1105.ꢀ
M.ꢀT.ꢀQuirós,ꢀM.ꢀP.ꢀMuñoz,ꢀJ.ꢀChristensenꢀandꢀS.ꢀColes,ꢀ
Organometallics,ꢀ2017,ꢀ36,ꢀ318.ꢀ
A.ꢀ González-Gómez,ꢀ G.ꢀ Dominguezꢀ andꢀ J.ꢀ Pérez-
Castells,ꢀEur.ꢀJ.ꢀOrg.ꢀChem.,ꢀ2009,ꢀ505.ꢀꢀ
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1
1,ꢀ521.ꢀꢀ
Q.ꢀ Qiao,ꢀ S.-S.ꢀ Soꢀ andꢀ R.ꢀ A.ꢀ Goodnow,ꢀ Jr.,ꢀ Org.ꢀ Lett.,ꢀ
001,ꢀ3,ꢀ3655.ꢀ
2
Forꢀ anꢀ exampleꢀ ofꢀ vinylcyclohexenesꢀ usedꢀ inꢀ theꢀ
synthesisꢀofꢀquinine,ꢀsee:ꢀP.ꢀWebberꢀandꢀM.ꢀJ.ꢀKrische,ꢀ
J.ꢀOrg.ꢀChem.,ꢀ2008,ꢀ73,ꢀ9379.ꢀꢀ
3
4
Forꢀ selectedꢀ examplesꢀ ofꢀ substitutedꢀ 7-memberedꢀ
ringsꢀinꢀtheꢀcoreꢀofꢀnaturalꢀproducts,ꢀsee:ꢀW.ꢀA.ꢀAyerꢀ
andꢀ E.ꢀ R.ꢀ Cruz,ꢀ J.ꢀ Org.ꢀ Chem.,ꢀ 1993,ꢀ 58,ꢀ 7529.ꢀ Forꢀ aꢀ
synthesisꢀofꢀtremulenolideꢀAꢀandꢀtremulenediolꢀA,ꢀsee:ꢀ
H.ꢀM.ꢀLꢀDaviesꢀandꢀB.ꢀD.ꢀDoan,ꢀJ.ꢀOrg.ꢀChem.,ꢀ1998,ꢀ63,ꢀ
6
57;ꢀ E.ꢀ L.ꢀ Ghisalberti,ꢀ Phytochemistry,ꢀ 1994,ꢀ 37,ꢀ 597.ꢀ
Forꢀaꢀsynthesisꢀofꢀtheꢀcarotaneꢀ(+)-schisanwilsoneneꢀA,ꢀ
see:ꢀM.ꢀGaydou,ꢀR.ꢀE.ꢀMiller,ꢀN.ꢀDelpont,ꢀJ.ꢀCecconꢀandꢀ
A.ꢀ M.ꢀ Echavarren,ꢀ Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.,ꢀ 2013,ꢀ 52,ꢀ
6
396.ꢀ Forꢀ aꢀ recentꢀ totalꢀ synthesisꢀ ofꢀ (±)-
dihydroisosubamol,ꢀsee:ꢀD.ꢀPflästerer,ꢀM.ꢀRudolph,ꢀB.ꢀF.ꢀ
Yates,ꢀ A.ꢀ Ariafardꢀ andꢀ A.ꢀ S.ꢀ K.ꢀ Hashmi,ꢀ Adv.ꢀ Synth.ꢀ
Catal.,ꢀ 2017,ꢀ 359,ꢀ 866.ꢀ Forꢀ aꢀ reviewꢀ onꢀ syntheticꢀ
strategiesꢀtoꢀaccessꢀ7-memberedꢀcarbocycles,ꢀsee:ꢀT.ꢀV.ꢀ
Nguyen,ꢀ J.ꢀ M.ꢀ Hartmannꢀ andꢀ D.ꢀ Enders,ꢀ Synthesis,ꢀ
2
013,ꢀ45,ꢀ845.ꢀ
ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ7ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

ROH
TsN
Organic & Biomolecular Che mP ias gt re y8 of 8
TsN
•
H
OR
OH
[
Pt(II)]
[Pt(II)]
TsN
TsN
TsN
solvent,
0˚C
R = H
solvent,
70˚C
R = alkyl
7
•
OH
OR
DivergenciesꢀunravelledꢀinꢀnewꢀPt-catalysedꢀalkoxy-ꢀandꢀ
hydroxycyclisaꢁonꢀofꢀN-tetherꢀ1,5-bisallenesꢀtoꢀgiveꢀvinyl-
tetrahydropyridinesꢀwithꢀalcoholsꢀandꢀhydro-1H-azepinesꢀwithꢀwater.