We analyzed the ligand electronic effect in a gold(i)-catalyzed intramolecular alkyne hydroamination, through a DFT and charge-displacement function (CDF) study. We found that, in the presence of π-electron conjugation between the alkyne and the nucleophilic functionality, electron poor ligands modify the coordination mode and the geometric parameters of the substrate in such a way that, contrary to expectations, the activation barrier of the nucleophilic attack increases. This remarkable effect is due to the competition between alkyne activation and nucleophile deactivation. The general relevance of these findings is highlighted.
Anomalous ligand effect in gold(I)-catalyzed intramolecular hydroamination of alkynes
GAGGIOLI, CARLO ALBERTO;CIANCALEONI, Gianluca;BISTONI, GIOVANNI;BELPASSI, LEONARDO;BELANZONI, Paola;TARANTELLI, Francesco
2015
Abstract
We analyzed the ligand electronic effect in a gold(i)-catalyzed intramolecular alkyne hydroamination, through a DFT and charge-displacement function (CDF) study. We found that, in the presence of π-electron conjugation between the alkyne and the nucleophilic functionality, electron poor ligands modify the coordination mode and the geometric parameters of the substrate in such a way that, contrary to expectations, the activation barrier of the nucleophilic attack increases. This remarkable effect is due to the competition between alkyne activation and nucleophile deactivation. The general relevance of these findings is highlighted.File in questo prodotto:
Non ci sono file associati a questo prodotto.
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.