om7b00668_si_001.pdf (44.11 MB)
Role of σ,π-Digold(I) Alkyne Complexes in Reactions of Enynes
journal contribution
posted on 2017-12-19, 16:19 authored by Sofia Ferrer, Antonio M. EchavarrenGold(I)
acetylide and σ,π-digold(I) alkyne complexes
derived from one prototypical 1,6-enyne and from 7-ethynyl-1,3,5-cycloheptatriene
have been prepared and structurally characterized. Their possible
role in gold(I)-catalyzed cycloisomerizations has been studied by
experiment and by DFT calculations. Gold(I) acetylides are totally
unproductive complexes in the absence of Brønsted acids. Similarly,
no cyclizations were observed by heating σ,π-digold(I)
alkyne digold(I) at least up to 130 °C. Theoretical studies provide
a rationale for the much lower reactivity of digold species in reactions
of enynes.