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

Ming Zhong Wang, Cong Ying Zhou, Zhen Guo, Ella Lai Ming Wong, Man Kin Wong, Chi Ming Che

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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 AuI-AuIinteractions. 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 (r2=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 AuIspecies. 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 AuI-AuIinteractions 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 AuI-AuIinteraction plays a key role in affecting the enatioselectivity of the reaction. KGaA, Weinheim.
Original languageEnglish
Pages (from-to)812-824
Number of pages13
JournalChemistry - An Asian Journal
Issue number3
Publication statusPublished - 1 Mar 2011


  • allenes
  • enantioselectivity
  • gold
  • hydroarylation
  • indoles

ASJC Scopus subject areas

  • Chemistry(all)

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