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Experimental and computational evidence for gold vinylidenes: generation from terminal alkynes via a bifurcation pathway and facile C-H insertions.


ABSTRACT: Facile cycloisomerization of (2-ethynylphenyl)alkynes is proposed to be promoted synergistically by two molecules of BrettPhosAuNTf(2), affording tricyclic indenes in mostly good yields. A gold vinylidene is most likely generated as one of the reaction intermediates on the basis of both mechanistic studies and theoretical calculations. Different from the well-known Rh, Ru, and W counterparts, this novel gold species is highly reactive and undergoes facile intramolecular C(sp(3))-H insertions as well as O-H and N-H insertions. The formation step for the gold vinylidene is predicted theoretically to be complex with a bifurcated reaction pathway. A pyridine N-oxide acts as a weak base to facilitate the formation of an alkynylgold intermediate, and the bulky BrettPhos ligand in the gold catalyst likely plays a role in sterically steering the reaction toward formation of the gold vinylidene.

SUBMITTER: Ye L 

PROVIDER: S-EPMC3257394 | biostudies-literature | 2012 Jan

REPOSITORIES: biostudies-literature

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Experimental and computational evidence for gold vinylidenes: generation from terminal alkynes via a bifurcation pathway and facile C-H insertions.

Ye Longwu L   Wang Yanzhao Y   Aue Donald H DH   Zhang Liming L  

Journal of the American Chemical Society 20111228 1


Facile cycloisomerization of (2-ethynylphenyl)alkynes is proposed to be promoted synergistically by two molecules of BrettPhosAuNTf(2), affording tricyclic indenes in mostly good yields. A gold vinylidene is most likely generated as one of the reaction intermediates on the basis of both mechanistic studies and theoretical calculations. Different from the well-known Rh, Ru, and W counterparts, this novel gold species is highly reactive and undergoes facile intramolecular C(sp(3))-H insertions as  ...[more]

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