1254470-34-2Relevant academic research and scientific papers
Gold(III)-catalyzed enynamine-cyclopentadiene cycloisomerization with chirality transfer: An experimental and theoretical study indicating involvement of dual au(iii) push-pull assisted cis - Trans isomerism
Wirtanen, Tom,Muuronen, Mikko,Melchionna, Michele,Patzschke, Michael,Helaja, Juho
, p. 10269 - 10283 (2014)
A synthetic approach for asymmetric ring-fused cyclopentadienes (Cps) with a chiral carbon at the ring junction has been established from chiral enynamines by achiral Au(III) catalysis. On the basis of experimental and theoretical data, the proposed mechanistic pathway from enynamines to Cps occurs via a Au(III) ene cis-trans isomerization step. Computational studies at DFT and NEVPT2 levels advocate that the cis-trans isomerization step proceeds via a dual Au(III) push-pull assisted intermediate with a low computed rotation barrier. The chirality transfer occurs through a helical-shaped transition state with allenic character. The scope of the catalysis encompasses sterically bulky enynamines including terpene natural products.
Isolation of a zwitterionic dienegold(III) Complex intermediate in the direct conversion of enyne-amines to cyclopentadienes
Melchionna, Michele,Nieger, Martin,Helaja, Juho
supporting information; experimental part, p. 8262 - 8267 (2010/09/03)
(Figure Presented) Golden ring: A route for the direct AuCl 3-catalyzed conversion of an enyne-amine into cyclopentadiene is reported. The mechanism for the catalysis is proposed and supported by a resting-state zwitterionic gold(III)cyclopentadiene structure (see figure).
