TY - JOUR
T1 - Cyclization of 2-Alkynyldimethylaniline on Gold(I) Cationic and Neutral Complexes
AU - Biasiolo, Luca
AU - Belpassi, Leonardo
AU - Gaggioli, Carlo Alberto
AU - MacChioni, Alceo
AU - Tarantelli, Francesco
AU - Ciancaleoni, Gianluca
AU - Zuccaccia, Daniele
N1 - Publisher Copyright:
© 2016 American Chemical Society.
Copyright:
Copyright 2016 Elsevier B.V., All rights reserved.
PY - 2016/2/22
Y1 - 2016/2/22
N2 - The cyclization reaction of 2-(1-hexynyl)dimethylaniline (S) on gold(I) has been studied by NMR spectroscopy, in order to characterize the ion pair structure of the product, [LAuSc]BF4. The latter is a good model for the catalytic intermediate between the nucleophilic attack and the protodeauration step of a typical gold catalytic cycle. 19F, 1H HOESY NMR results demonstrate that in [LAuSc]BF4, with L being three different ligands, the anion mainly interacts with the ammonium moiety of the substrate, thanks to its formal positive charge, even if the ligand can tune the exact position of the anion. Furthermore, also gold chloride is able to promote the cyclization of S, forming [ClAuSc], which is the first example of a new class of precatalysts with potentially interesting catalytic properties. Preliminary data on its catalytic performances and a detailed DFT characterization of its electronic properties are presented, both of which indicate that Sc behaves as a carbene.
AB - The cyclization reaction of 2-(1-hexynyl)dimethylaniline (S) on gold(I) has been studied by NMR spectroscopy, in order to characterize the ion pair structure of the product, [LAuSc]BF4. The latter is a good model for the catalytic intermediate between the nucleophilic attack and the protodeauration step of a typical gold catalytic cycle. 19F, 1H HOESY NMR results demonstrate that in [LAuSc]BF4, with L being three different ligands, the anion mainly interacts with the ammonium moiety of the substrate, thanks to its formal positive charge, even if the ligand can tune the exact position of the anion. Furthermore, also gold chloride is able to promote the cyclization of S, forming [ClAuSc], which is the first example of a new class of precatalysts with potentially interesting catalytic properties. Preliminary data on its catalytic performances and a detailed DFT characterization of its electronic properties are presented, both of which indicate that Sc behaves as a carbene.
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U2 - 10.1021/acs.organomet.5b01030
DO - 10.1021/acs.organomet.5b01030
M3 - Article
AN - SCOPUS:84959126337
SN - 0276-7333
VL - 35
SP - 595
EP - 604
JO - Organometallics
JF - Organometallics
IS - 4
ER -