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Intramolecular CH Activation through Gold(I)‐Catalyzed Reaction of Iodoalkynes
Author(s) -
MoránPoladura Pablo,
Rubio Eduardo,
González José M.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201409970
Subject(s) - cycloisomerization , indene , chemistry , catalysis , alkyne , intramolecular force , medicinal chemistry , yield (engineering) , isomerization , carbon–carbon bond , photochemistry , stereochemistry , organic chemistry , materials science , metallurgy
The cycloisomerization reaction of 1‐(iodoethynyl)‐2‐(1‐methoxyalkyl)arenes and related 2‐alkyl‐substituted derivatives gives the corresponding 3‐iodo‐1‐substituted‐1 H ‐indene under the catalytic influence of IPrAuNTf 2 [IPr=1,3‐bis(2,6‐diisopropyl)phenylimidazol‐2‐ylidene; NTf 2 =bis(trifluoromethanesulfonyl)imidate]. The reaction takes place in 1,2‐dichloroethane at 80 °C, and the addition of ttbp (2,4,6‐tri‐ tert ‐butylpyrimidine) is beneficial to accomplish this new transformation in high yield. The overall reaction implies initial assembly of an intermediate gold vinylidene upon alkyne activation by gold(I) and a 1,2‐iodine‐shift. Deuterium labeling and crossover experiments, the magnitude of the recorded kinetic primary isotopic effect, and the results obtained from the reaction of selected stereochemical probes strongly provide support for concerted insertion of the benzylic CH bond into gold vinylidene as the step responsible for the formation of the new carbon–carbon bond.