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Article: Gold(I)-catalyzed enantioselective intermolecular hydroarylation of allenes with indoles and reaction mechanism by density functional theory calculations
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TitleGold(I)-catalyzed enantioselective intermolecular hydroarylation of allenes with indoles and reaction mechanism by density functional theory calculations
 
AuthorsWang, MZ1
Zhou, CY1
Guo, Z1
Wong, ELM1
Wong, MK1 2
Che, CM1
 
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
 
CitationChemistry - An Asian Journal, 2011, v. 6 n. 3, p. 812-824 [How to Cite?]
DOI: http://dx.doi.org/10.1002/asia.201000651
 
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.
 
ISSN1861-4728
2013 Impact Factor: 3.935
2013 SCImago Journal Rankings: 1.861
 
DOIhttp://dx.doi.org/10.1002/asia.201000651
 
ISI Accession Number IDWOS:000288095500012
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.

 
ReferencesReferences in Scopus
 
GrantsReactive Metal-Ligand Multiple Bonded Complexes. From Biomimetic Reactions to Highly Efficient Chemical Synthesis
Institute of molecular technology for drug discovery and synthesis
 
DC FieldValue
dc.contributor.authorWang, MZ
 
dc.contributor.authorZhou, CY
 
dc.contributor.authorGuo, Z
 
dc.contributor.authorWong, ELM
 
dc.contributor.authorWong, MK
 
dc.contributor.authorChe, CM
 
dc.date.accessioned2011-06-17T09:18:33Z
 
dc.date.available2011-06-17T09:18:33Z
 
dc.date.issued2011
 
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.
 
dc.description.naturelink_to_subscribed_fulltext
 
dc.identifier.citationChemistry - An Asian Journal, 2011, v. 6 n. 3, p. 812-824 [How to Cite?]
DOI: http://dx.doi.org/10.1002/asia.201000651
 
dc.identifier.doihttp://dx.doi.org/10.1002/asia.201000651
 
dc.identifier.epage824
 
dc.identifier.hkuros185664
 
dc.identifier.isiWOS:000288095500012
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.

 
dc.identifier.issn1861-4728
2013 Impact Factor: 3.935
2013 SCImago Journal Rankings: 1.861
 
dc.identifier.issue3
 
dc.identifier.openurl
 
dc.identifier.pmid21344657
 
dc.identifier.scopuseid_2-s2.0-79951986436
 
dc.identifier.spage812
 
dc.identifier.urihttp://hdl.handle.net/10722/134357
 
dc.identifier.volume6
 
dc.languageeng
 
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/2451
 
dc.publisher.placeGermany
 
dc.relation.ispartofChemistry - An Asian Journal
 
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.relation.referencesReferences in Scopus
 
dc.subject.meshAlkadienes - chemistry
 
dc.subject.meshCatalysis
 
dc.subject.meshCrystallography, X-Ray
 
dc.subject.meshGold - chemistry
 
dc.subject.meshIndoles - chemistry
 
dc.subjectallenes
 
dc.subjectenantioselectivity
 
dc.subjectgold
 
dc.subjecthydroarylation
 
dc.subjectindoles
 
dc.titleGold(I)-catalyzed enantioselective intermolecular hydroarylation of allenes with indoles and reaction mechanism by density functional theory calculations
 
dc.typeArticle
 
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<description.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 &#963;. 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. &#169; 2011 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.</description.abstract>
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Author Affiliations
  1. Institute of Molecular Technology for Drug Discovery and Synthesis, Hong Kong
  2. Hong Kong Polytechnic University