Anomalous ligand effect in gold(I)-catalyzed intramolecular hydroamination of alkynes

Chemical Communications : Chem Comm
Carlo Alberto GaggioliFrancesco Tarantelli

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.

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Citations

Jan 30, 2016·Journal of Chemical Theory and Computation·Giovanni BistoniFrancesco Tarantelli
Oct 2, 2015·Chemical Reviews·Kunbing OuyangZhenfeng Xi
Mar 1, 2017·Chemistry : a European Journal·Sebastian ArndtA Stephen K Hashmi
Jan 9, 2020·Physical Chemistry Chemical Physics : PCCP·Elisa RossiPaola Belanzoni
Dec 18, 2020·The Journal of Physical Chemistry. a·Diego SorbelliLeonardo Belpassi
Oct 24, 2017·The Journal of Organic Chemistry·Nadezhda M VitkovskayaBoris A Trofimov
May 10, 2018·Inorganic Chemistry·Diego SorbelliPaola Belanzoni
Feb 1, 2018·Journal of Chemical Theory and Computation·Matteo De SantisLoriano Storchi

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