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Article: Gold(I)-catalyzed enantioselective intermolecular hydroarylation of allenes with indoles and reaction mechanism by density functional theory calculations

TitleGold(I)-catalyzed enantioselective intermolecular hydroarylation of allenes with indoles and reaction mechanism by density functional theory calculations
Authors
Keywordsallenes
enantioselectivity
gold
hydroarylation
indoles
Issue Date2011
PublisherWiley - V C H Verlag GmbH & Co. KGaA. The Journal's web site is located at http://www.wiley-vch.de/publish/en/journals/alphabeticIndex/2451
Citation
Chemistry - An Asian Journal, 2011, v. 6 n. 3, p. 812-824 How to Cite?
Abstract
Chiral binuclear gold(I) phosphine complexes catalyze enantioselective intermolecular hydroarylation of allenes with indoles in high product yields (up to 90 %) and with moderate enantioselectivities (up to 63%ee). Among the gold(I) complexes examined, better ee values were obtained with binuclear gold(I) complexes, which displayed intramolecular Au I-Au I interactions. The binuclear gold(I) complex 4 c [(AuCl) 2(L3)] with chiral biaryl phosphine ligand (S)-(-)-MeO-biphep (L3) is the most efficient catalyst and gives the best ee value of up to 63 %. Substituents on the allene reactants have a slight effect on the enantioselectivity of the reaction. Electron-withdrawing groups on the indole substrates decrease the enantioselectivity of the reaction. The relative reaction rates of the hydroarylation of 4-X-substituted 1,3-diarylallenes with N-methylindole in the presence of catalyst 4 c [(AuCl) 2(L3)]/AgOTf [L3=(S)-(-)-MeO-biphep], determined through competition experiments, correlate (r 2=0.996) with the substituent constants σ. The slope value is -2.30, revealing both the build-up of positive charge at the allene and electrophilic nature of the reactive Au I species. Two plausible reaction pathways were investigated by density functional theory calculations, one pathway involving intermolecular nucleophilic addition of free indole to aurated allene intermediate and another pathway involving intramolecular nucleophilic addition of aurated indole to allene via diaurated intermediate E2. Calculated results revealed that the reaction likely proceeds via the first pathway with a lower activation energy. The role of Au I-Au I interactions in affecting the enantioselectivity is discussed. It has a certain aura about it: An enantioselective intermolecular hydroarylation of allenes with indole, catalyzed by a chiral binuclear gold(I) phosphine complex, was developed. DFT calculations revealed that the reaction proceeds through nucleophilic addition of free indole to monoaurated allene intermediate rather than diaurated species, and the intramolecular Au I-Au I interaction plays a key role in affecting the enatioselectivity of the reaction. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Persistent Identifierhttp://hdl.handle.net/10722/134357
ISSN
2013 Impact Factor: 3.935
2013 SCImago Journal Rankings: 1.861
ISI Accession Number ID
Funding AgencyGrant Number
University of Hong Kong
Hong Kong Research Grant CouncilPolyU 5027/09P
University Grants Committee of the Hong Kong Special Administrative Region, ChinaAoE/P-10/01
RGCHKU1/CRF/08
HKU 7007/08P
Funding Information:

We are thankful for the financial support of The University of Hong Kong (University Development Fund), Hong Kong Research Grant Council (PolyU 5027/09P), the Areas of Excellence Scheme established under the University Grants Committee of the Hong Kong Special Administrative Region, China (AoE/P-10/01), RGC Collaborative Research Fund (HKU1/CRF/08), and RGC grant (HKU 7007/08P). We thank Dr. Stephen Sin-Yin Chui and Dr. Nianyong Zhu for solving the X-ray crystal structures.

References
Grants

 

DC FieldValueLanguage
dc.contributor.authorWang, MZen_HK
dc.contributor.authorZhou, CYen_HK
dc.contributor.authorGuo, Zen_HK
dc.contributor.authorWong, ELMen_HK
dc.contributor.authorWong, MKen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2011-06-17T09:18:33Z-
dc.date.available2011-06-17T09:18:33Z-
dc.date.issued2011en_HK
dc.identifier.citationChemistry - An Asian Journal, 2011, v. 6 n. 3, p. 812-824en_HK
dc.identifier.issn1861-4728en_HK
dc.identifier.urihttp://hdl.handle.net/10722/134357-
dc.description.abstractChiral binuclear gold(I) phosphine complexes catalyze enantioselective intermolecular hydroarylation of allenes with indoles in high product yields (up to 90 %) and with moderate enantioselectivities (up to 63%ee). Among the gold(I) complexes examined, better ee values were obtained with binuclear gold(I) complexes, which displayed intramolecular Au I-Au I interactions. The binuclear gold(I) complex 4 c [(AuCl) 2(L3)] with chiral biaryl phosphine ligand (S)-(-)-MeO-biphep (L3) is the most efficient catalyst and gives the best ee value of up to 63 %. Substituents on the allene reactants have a slight effect on the enantioselectivity of the reaction. Electron-withdrawing groups on the indole substrates decrease the enantioselectivity of the reaction. The relative reaction rates of the hydroarylation of 4-X-substituted 1,3-diarylallenes with N-methylindole in the presence of catalyst 4 c [(AuCl) 2(L3)]/AgOTf [L3=(S)-(-)-MeO-biphep], determined through competition experiments, correlate (r 2=0.996) with the substituent constants σ. The slope value is -2.30, revealing both the build-up of positive charge at the allene and electrophilic nature of the reactive Au I species. Two plausible reaction pathways were investigated by density functional theory calculations, one pathway involving intermolecular nucleophilic addition of free indole to aurated allene intermediate and another pathway involving intramolecular nucleophilic addition of aurated indole to allene via diaurated intermediate E2. Calculated results revealed that the reaction likely proceeds via the first pathway with a lower activation energy. The role of Au I-Au I interactions in affecting the enantioselectivity is discussed. It has a certain aura about it: An enantioselective intermolecular hydroarylation of allenes with indole, catalyzed by a chiral binuclear gold(I) phosphine complex, was developed. DFT calculations revealed that the reaction proceeds through nucleophilic addition of free indole to monoaurated allene intermediate rather than diaurated species, and the intramolecular Au I-Au I interaction plays a key role in affecting the enatioselectivity of the reaction. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.en_HK
dc.languageengen_US
dc.publisherWiley - V C H Verlag GmbH & Co. KGaA. The Journal's web site is located at http://www.wiley-vch.de/publish/en/journals/alphabeticIndex/2451en_HK
dc.relation.ispartofChemistry - An Asian Journalen_HK
dc.subjectallenesen_HK
dc.subjectenantioselectivityen_HK
dc.subjectgolden_HK
dc.subjecthydroarylationen_HK
dc.subjectindolesen_HK
dc.subject.meshAlkadienes - chemistry-
dc.subject.meshCatalysis-
dc.subject.meshCrystallography, X-Ray-
dc.subject.meshGold - chemistry-
dc.subject.meshIndoles - chemistry-
dc.titleGold(I)-catalyzed enantioselective intermolecular hydroarylation of allenes with indoles and reaction mechanism by density functional theory calculationsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1861-4728&volume=6&issue=3&spage=812&epage=824&date=2011&atitle=Gold(I)-catalyzed+enantioselective+intermolecular+hydroarylation+of+allenes+with+indoles+and+reaction+mechanism+by+density+functional+theory+calculations-
dc.identifier.emailZhou, CY:cyzhou@hku.hken_HK
dc.identifier.emailWong, ELM:wongella@hku.hken_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.authorityZhou, CY=rp00843en_HK
dc.identifier.authorityWong, ELM=rp00807en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/asia.201000651en_HK
dc.identifier.pmid21344657-
dc.identifier.scopuseid_2-s2.0-79951986436en_HK
dc.identifier.hkuros185664en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-79951986436&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume6en_HK
dc.identifier.issue3en_HK
dc.identifier.spage812en_HK
dc.identifier.epage824en_HK
dc.identifier.isiWOS:000288095500012-
dc.publisher.placeGermanyen_HK
dc.relation.projectReactive Metal-Ligand Multiple Bonded Complexes. From Biomimetic Reactions to Highly Efficient Chemical Synthesis-
dc.relation.projectInstitute of molecular technology for drug discovery and synthesis-
dc.identifier.scopusauthoridWang, MZ=15125218300en_HK
dc.identifier.scopusauthoridZhou, CY=35742480200en_HK
dc.identifier.scopusauthoridGuo, Z=36554069300en_HK
dc.identifier.scopusauthoridWong, ELM=8944839700en_HK
dc.identifier.scopusauthoridWong, MK=7403908449en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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