Journal of the American Chemical Society
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ee).ꢀ ꢀ ꢀ Thisꢀ isꢀ theꢀ firstꢀ successfulꢀ exampleꢀ ofꢀ theꢀ transitionꢀ
metal-catalyzedꢀ enantioselectiveꢀ propargylicꢀ etherification.ꢀꢀꢀ
Propargylicꢀ carbonateꢀ wasꢀ revealedꢀ toꢀ beꢀ aꢀ substrateꢀ ofꢀ
choice.ꢀ ꢀ ꢀ Itꢀ isꢀ noteworthyꢀ thatꢀ aꢀ varietyꢀ ofꢀ propargylicꢀ car-
bonatesꢀbearingꢀanꢀalkylꢀsubstituentꢀatꢀtheꢀpropargylicꢀposi-
tionꢀareꢀapplicableꢀasꢀsubstratesꢀinꢀtheꢀpresentꢀreactionꢀsys-
tem.ꢀꢀFurtherꢀstudiesꢀonꢀtheꢀtransitionꢀmetal-catalyzedꢀenan-
tioselectiveꢀ propargylicꢀ substitutionꢀ reactionsꢀ withꢀ otherꢀ
nucleophilesꢀareꢀcurrentlyꢀinꢀprogress.ꢀꢀꢀ
2008,ꢀ47,ꢀ3777.ꢀ(b)ꢀDetz,ꢀR.ꢀJ.;ꢀAbiri,ꢀZ.;ꢀleꢀGriel,ꢀR.;ꢀHiemstra,ꢀH.;ꢀvanꢀ
Maarseveen,ꢀJ.ꢀH.ꢀChem.ꢀEur.ꢀJ.ꢀ2011,ꢀ17,ꢀ5921.ꢀ
7)ꢀ Cu-catalyzedꢀ enantioselectiveꢀ propargylicꢀ substitutionꢀ reac-
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(
tionsꢀbyꢀHuꢀandꢀco-workers;ꢀꢀ(a)ꢀZhang,ꢀC.;ꢀWang,ꢀY.-H.;ꢀHu,ꢀX.-H.;ꢀ
Zheng,ꢀ Z.;ꢀ Xu,ꢀ J.;ꢀ Hu,ꢀ X.-P.ꢀ Adv.ꢀ Synth.ꢀ Catal.ꢀ 2012,ꢀ 354,ꢀ 2854.ꢀ (b)ꢀ
Zhang,ꢀC.;ꢀHu,ꢀX.-H.;ꢀWang,ꢀY.-H.;ꢀZheng,ꢀZ.;ꢀXu,ꢀJ.;ꢀHu,ꢀX.-P.ꢀJ.ꢀAm.ꢀ
Chem.ꢀ Soc.ꢀ 2012,ꢀ134,ꢀ9585.ꢀ(c)ꢀHan,ꢀF.-Z.;ꢀZhu,ꢀF.-L.;ꢀWang,ꢀY.-H.;ꢀ
Zou,ꢀY.;ꢀHu,ꢀX.-H.;ꢀChen,ꢀS.;ꢀHu,ꢀX.-P.ꢀOrg.ꢀ Lett.ꢀ2014,ꢀ16,ꢀ588.ꢀ(d)ꢀ
Zhu,ꢀF.-L.;ꢀZou,ꢀY.;ꢀZhang,ꢀD.-Y.;ꢀWang,ꢀY.-H.;ꢀHu,ꢀX.-H.;ꢀChen,ꢀS.;ꢀ
Xu,ꢀJ.;ꢀHu,ꢀX.-P.ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀ2014,ꢀ53,ꢀ1410.ꢀ(e)ꢀZou,ꢀY.;ꢀZhu,ꢀ
F.-L.;ꢀDuan,ꢀZ.-C.;ꢀWang,ꢀY.-H.;ꢀZhang,ꢀD.-Y.;ꢀCao,ꢀZ.;ꢀZheng,ꢀZ.;ꢀHu,ꢀ
X.-P.ꢀ Tetrahedronꢀ Lett.ꢀ 2014,ꢀ 55,ꢀ 2033.ꢀ (f)ꢀ Zhu,ꢀ F.-L.;ꢀ Wang,ꢀ Y.-H.;ꢀ
Zhang,ꢀD.-Y.;ꢀHu,ꢀX.-H.;ꢀChen,ꢀS.;ꢀHou,ꢀS.-J.;ꢀXu,ꢀJ.;ꢀHu,ꢀX.-P.ꢀAdv.ꢀ
Synth,.ꢀCatal.ꢀ2014,ꢀ356,ꢀ3231.ꢀ(g)ꢀZhu,ꢀF.-L.;ꢀWang,ꢀY.-H.;ꢀZhang,ꢀD.-
Y.;ꢀXu,ꢀJ.;ꢀHu,ꢀX.-P.ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀ2014,ꢀ53,ꢀ10223.ꢀ(h)ꢀZhang,ꢀ
D.-Y.;ꢀZhu,ꢀF.-L.;ꢀWang,ꢀY.-H.;ꢀHu,ꢀX.-H.;ꢀChen,ꢀS.;ꢀHou,ꢀC.-J.;ꢀHu,ꢀX.-
P.ꢀChem.ꢀCommun.ꢀ2014,ꢀ50,ꢀ14459.ꢀꢀ
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Supporting Information
Experimentalꢀprocedures,ꢀspectroscopicꢀdata,ꢀandꢀX-rayꢀdataꢀ
(
CIF).ꢀꢀꢀThisꢀmaterialꢀisꢀavailableꢀfreeꢀofꢀchargeꢀviaꢀtheꢀInter-
netꢀatꢀhttp://pubs.acs.org.ꢀ
(
8)ꢀ Cu-catalyzedꢀ enantioselectiveꢀ propargylicꢀ substitutionꢀ reac-
tionsꢀ byꢀ otherꢀ researchꢀ groups;ꢀ (a)ꢀ Fang,ꢀ P.;ꢀ Hou,ꢀ X.-L.ꢀ Org.ꢀ Lett.ꢀ
2009,ꢀ11,ꢀ4612.ꢀ(b)ꢀMino,ꢀT.;ꢀTaguchi,ꢀH.;ꢀHashimoto,ꢀM.;ꢀSakamoto,ꢀ
N.ꢀTetrahedron:ꢀAsymmetryꢀ2013,ꢀ24,ꢀ1520.ꢀ(c)ꢀZhai,ꢀL.;ꢀHuang,ꢀG.-X.;ꢀ
Guo,ꢀB.-B.;ꢀXu,ꢀL.-J.;ꢀChen,ꢀJ.;ꢀCao,ꢀW.-G.;ꢀZhai,ꢀG.;ꢀWu,ꢀX.-Y.ꢀOrg.ꢀ
Lett.ꢀ2014,ꢀ16,ꢀ5584.ꢀ(d)ꢀWang,ꢀB.;ꢀLiu,ꢀC.;ꢀGuo,ꢀH.ꢀRSCꢀAdv.ꢀ2014,ꢀ4,ꢀ
AUTHOR INFORMATION
Corresponding Author
ynishiba@sogo.t.u-tokyo.ac.jpꢀ
5
3216.ꢀꢀ
9)ꢀLewisꢀacid-catalyzedꢀenantioselectiveꢀpropargylicꢀsubstitutionꢀ
(
ACKNOWLEDGMENT
reactionsꢀofꢀpropargylicꢀalcoholsꢀbearingꢀanꢀinternalꢀalkyneꢀmoiety;ꢀ
(a)ꢀMotoyama,ꢀK.;ꢀIkeda,ꢀM.;ꢀMiyake,ꢀY.;ꢀNishibayashi,ꢀY.ꢀEur.ꢀJ.ꢀOrg.ꢀ
Chem.ꢀ2011,ꢀ2239.ꢀ(b)ꢀSinisi,ꢀR.;ꢀVita,ꢀM.ꢀV.;ꢀGualandi,ꢀA.;ꢀEmer,ꢀE.;ꢀ
Cozzi,ꢀP.ꢀG.ꢀChem.ꢀEur.ꢀJ.ꢀ2011,ꢀ17,ꢀ7404.ꢀꢀ
Weꢀ thankꢀ Grants-in-Aidꢀ forꢀ Scientificꢀ Researchꢀ (Nos.ꢀ
2
6288044,ꢀ26620075,ꢀ26105708,ꢀandꢀ26870120)ꢀfromꢀtheꢀJapanꢀ
SocietyꢀforꢀtheꢀPromotionꢀofꢀScienceꢀ(JSPS)ꢀandꢀtheꢀMinistryꢀ
ofꢀ Education,ꢀ Culture,ꢀ Sports,ꢀ Scienceꢀ andꢀ Technologyꢀ ofꢀ
Japanꢀ(MEXT).ꢀꢀꢀꢀ
(
10)ꢀPreparationꢀandꢀcharacterizationꢀofꢀdicopper-pyboxꢀcomplexꢀ
[
Cu (L2) ][PF ] ꢀ haveꢀ alreadyꢀ beenꢀ reportedꢀ byꢀ Gamasaꢀ andꢀ co-
2
2
6 2
workers;ꢀ(a)ꢀDíez,ꢀJ.;ꢀGamasa,ꢀM.ꢀP.;ꢀPanera,ꢀM.ꢀInorg.ꢀChem.ꢀ2006,ꢀ
45,ꢀ10043.ꢀ(b)ꢀPanera,ꢀM.;ꢀDíez,ꢀJ.;ꢀMerino,ꢀI.;ꢀRubio,ꢀE.;ꢀGamasa,ꢀM.ꢀP.ꢀ
Inorg.ꢀ Chem.ꢀ 2009,ꢀ 48,ꢀ 11147.ꢀ (c)ꢀ Gamasaꢀ andꢀ co-workersꢀ reportedꢀ
thatꢀ [Cu (L3) ][PF ] ꢀ reactedꢀ withꢀ NaClꢀ gaveꢀ theꢀ correspondingꢀ
REFERENCES
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chloride-bridgedꢀdicopperꢀcomplexꢀhasꢀtwoꢀtetrahedralꢀcoordinationꢀ
copperꢀ moieties,ꢀ whereꢀ bothꢀ copperꢀ moietiesꢀ canꢀ workꢀ asꢀ reactiveꢀ
sites.ꢀ ꢀ ꢀ Basedꢀ onꢀ theꢀ result,ꢀ weꢀ considerꢀ thatꢀ aꢀ similarꢀ copper-
acetylideꢀcomplexꢀsuchꢀasꢀAꢀmayꢀbeꢀformedꢀfromꢀtheꢀreactionꢀofꢀ5ꢀ
withꢀpropargylicꢀcarbonate.ꢀꢀꢀꢀ
Hawker,ꢀC.ꢀJ.;ꢀWooley,ꢀK.ꢀL.ꢀScienceꢀ2005,ꢀ309,ꢀ1200.ꢀ(e)ꢀMoses,ꢀJ.ꢀE.;ꢀ
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(
2)ꢀNishibayashi,ꢀY.;ꢀOnodera,ꢀG.;ꢀInada,ꢀY.;ꢀHidai,ꢀM.;ꢀUemura,ꢀS.ꢀ
Organometallicsꢀ2003,ꢀ22,ꢀ873.ꢀꢀ
3)ꢀForꢀreviewsꢀonꢀtheꢀtransitionꢀmetal-catalyzedꢀenantioselectiveꢀ
(
11)ꢀSeeꢀtheꢀSupportingꢀInformationꢀinꢀdetails.ꢀ
(12)ꢀ Satyanarayana,ꢀ T.;ꢀ Abraham,ꢀ S.;ꢀ Kagan,ꢀ H.ꢀ B.ꢀ Angew.ꢀ Chem.ꢀ
Int.ꢀEd.ꢀ2009,ꢀ48,ꢀ456.ꢀꢀ
(
propargylicꢀ substitutionꢀ reactionsꢀ byꢀ ourꢀ group;ꢀ (a)ꢀ Miyake,ꢀ Y.;ꢀ
Uemura,ꢀS.;ꢀNishibayashi,ꢀY.ꢀChemCatChemꢀ2009,ꢀ1,ꢀ342.ꢀ(b)ꢀNishi-
bayashi,ꢀY.ꢀSynthesisꢀ2012,ꢀ44,ꢀ489.ꢀForꢀrecentꢀreviewsꢀonꢀtheꢀtransi-
tionꢀ metal-catalyzedꢀ enantioselectiveꢀ propargylicꢀ substitutionꢀ reac-
tionsꢀbyꢀotherꢀresearchꢀgroups;ꢀ(c)ꢀLjungdahl,ꢀN.;ꢀKann,ꢀN.ꢀAngew.ꢀ
Chem.ꢀInt.ꢀEd.ꢀ2009,ꢀ48,ꢀ642.ꢀ(d)ꢀDetz,ꢀR.ꢀJ.;ꢀHiemstra,ꢀH.;ꢀvanꢀMaar-
seveen,ꢀJ.ꢀH.ꢀEur.ꢀJ.ꢀOrg.ꢀChem.ꢀ2009,ꢀ6263.ꢀ(e)ꢀDing,ꢀC-H.;ꢀHou,ꢀX.-L.ꢀ
Chem.ꢀRev.ꢀ2011,ꢀ111,ꢀ1914.ꢀ(f)ꢀZhang,ꢀD.-Y.;ꢀHu,ꢀZ.-P.ꢀTetrahedronꢀLett.ꢀ
(
13)ꢀCopper-allenylideneꢀcomplexesꢀhaveꢀnotꢀyetꢀbeenꢀisolatedꢀandꢀ
characterizedꢀuntilꢀnowꢀalthoughꢀsilver-ꢀandꢀgold-allynlideneꢀcom-
plexesꢀhaveꢀalreadyꢀbeenꢀreportedꢀbyꢀBertrandꢀandꢀHashmi,ꢀrespec-
tively.ꢀ (a)ꢀ Asay,ꢀ M.;ꢀ Donnadieu,ꢀ B.;ꢀ Schoeller,ꢀ W.ꢀ W.;ꢀ Bertrand,ꢀ G.ꢀ
Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.ꢀ 2009,ꢀ 48,ꢀ 4796.ꢀ (b)ꢀ Hansmann,ꢀ M.ꢀ M.;ꢀ
Rominger,ꢀF.;ꢀHashmi,ꢀA.ꢀS.ꢀK.ꢀChem.ꢀSci.ꢀ2013,ꢀ4,ꢀ1552.ꢀꢀꢀꢀ
(
14)ꢀ Manyꢀ typesꢀ ofꢀ polynuclearꢀ copper-acetylideꢀ complexesꢀ in-
cludingꢀdicopper-acetylideꢀcomplexesꢀhaveꢀsoꢀfarꢀbeenꢀisolatedꢀandꢀ
characterizedꢀbyꢀ X-rayꢀcrystallography.ꢀ (a)ꢀDíez,ꢀ J.;ꢀ Gamasa,ꢀ M.ꢀ P.;ꢀ
Gimeno,ꢀJ.;ꢀAguirre,ꢀA.;ꢀGarcía-Granda,ꢀS.;ꢀHolunova,ꢀJ.;ꢀFalvello,ꢀL.ꢀR.ꢀ
Organometallicsꢀ 1998,ꢀ 18,ꢀ 662.ꢀ (b)ꢀ Mealli,ꢀ C.;ꢀ Codinho,ꢀ S.ꢀ S.;ꢀ Cal-
horda,ꢀM.ꢀJ.ꢀOrganometallicsꢀ2001,ꢀ20,ꢀ1734.ꢀꢀ
2
015,ꢀ56,ꢀ283.ꢀꢀ
4)ꢀ Ru-catalyzedꢀ enantioselectiveꢀ propargylicꢀ substitutionꢀ reac-
(
tions;ꢀ(a)ꢀInada,ꢀY.;ꢀNishibayashi,ꢀY.;ꢀUemura,ꢀS.ꢀAngew.ꢀChem.ꢀInt.ꢀ
Ed.ꢀ 2005,ꢀ 44,ꢀ 7715.ꢀ (b)ꢀ Matsuzawa,ꢀ H.;ꢀ Miyake,ꢀ Y.;ꢀ Nishibayashi,ꢀ Y.ꢀ
Angew.ꢀChem.ꢀInt.ꢀEd.ꢀ2007,ꢀ46,ꢀ6488.ꢀ(c)ꢀFukamizu,ꢀK.;ꢀMiyake,ꢀY.;ꢀ
Nishibayashi,ꢀY.ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.ꢀ2008,ꢀ130,ꢀ10498.ꢀ(d)ꢀIkeda,ꢀM.;ꢀ
Miyake,ꢀY.;ꢀNishibayashi,ꢀY.ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀ2010,ꢀ49,ꢀ7289.ꢀ(e)ꢀ
Ikeda,ꢀM.;ꢀMiyake,ꢀY.;ꢀNishibayashi,ꢀY.ꢀChem.ꢀEur.ꢀJ.ꢀ2012,ꢀ18,ꢀ3321.ꢀꢀ
(
15)ꢀInꢀsharpꢀcontrastꢀtoꢀtheꢀproposedꢀreactionꢀpathwayꢀshownꢀinꢀ
Schemeꢀ3,ꢀweꢀelucidatedꢀtheꢀdetailedꢀreactionꢀpathwayꢀofꢀtheꢀcop-
per-catalyzedꢀpropargylicꢀaminationꢀbyꢀusingꢀL5,ꢀwhereꢀmononucle-
arꢀcopper-allenylideneꢀcomplexesꢀwereꢀproposedꢀbyꢀtheꢀkineticꢀstudyꢀ
andꢀ theꢀ DFTꢀ calculation,ꢀ includingꢀ theꢀ linerꢀ relationshipꢀ betweenꢀ
(
5)ꢀ Cu-catalyzedꢀ enantioselectiveꢀ propargylicꢀ substitutionꢀ reac-
tionsꢀbyꢀourꢀgroup;ꢀ(a)ꢀHattori,ꢀG.;ꢀMatsuzawa,ꢀH.;ꢀMiyake,ꢀY.;ꢀNishi-
bayashi,ꢀ Y.ꢀ Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.ꢀ 2008,ꢀ 47,ꢀ 3781.ꢀ (b)ꢀ Hattori,ꢀ G.;ꢀ
Yoshida,ꢀA.;ꢀMiyake,ꢀY.;ꢀNishibayashi,ꢀY.ꢀJ.ꢀOrg.ꢀChem.ꢀ2009,ꢀ74,ꢀ7603.ꢀ
5c
theꢀeeꢀvalueꢀofꢀL5ꢀandꢀtheꢀeeꢀvalueꢀofꢀproduct. ꢀꢀꢀWhenꢀweꢀconsid-
eredꢀtheꢀpreviousꢀstudyꢀonꢀtheꢀcopper-catalyzedꢀpropargylicꢀamina-
tion,ꢀ weꢀ canꢀ notꢀ excludeꢀ theꢀ possibilityꢀ thatꢀ mononuclearꢀ copper-
allenylideneꢀcomplexesꢀworkedꢀasꢀkeyꢀreactiveꢀintermediates.ꢀꢀꢀFur-
therꢀ investigationꢀ isꢀ necessaryꢀ toꢀ clarifyꢀ theꢀ detailedꢀ reactionꢀ
pathwayꢀofꢀtheꢀpresentꢀpropargylicꢀetherification.ꢀꢀꢀꢀ
(
c)ꢀ Hattori,ꢀ G.;ꢀ Sakata,ꢀ K.;ꢀ Matsuzawa,ꢀ H.;ꢀ Tanabe,ꢀ Y.;ꢀ Miyake,ꢀ Y.;ꢀ
Nishibayashi,ꢀY.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ2010,ꢀ132,ꢀ10592.ꢀ(d)ꢀShibata,ꢀM.;ꢀ
Nakajima,ꢀK.;ꢀNishibayashi,ꢀY.ꢀChem.ꢀCommun.ꢀ2014,ꢀ50,ꢀ7874.ꢀꢀ
(
6)ꢀ Cu-catalyzedꢀ enantioselectiveꢀ propargylicꢀ substitutionꢀ reac-
tionsꢀbyꢀvanꢀMaarseveenꢀandꢀco-workers;ꢀꢀ(a)ꢀDetz,ꢀR.ꢀJ.;ꢀDelville,ꢀM.ꢀ
M.ꢀ E.;ꢀ Hiemstra,ꢀ H.;ꢀ vanꢀ Maarseveen,ꢀ J.ꢀ H.ꢀ Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.ꢀ
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