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Alkyne Hydroarylations with Chelating Dicarbene Palladium(II) Complex Catalysts: Improved and Unexpected Reactivity Patterns Disclosed Upon Additive Screening
Author(s) -
Biffis Andrea,
Gazzola Luca,
Gobbo Pierangelo,
Buscemi Gabriella,
Tubaro Cristina,
Basato Marino
Publication year - 2009
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200900321
Subject(s) - chemistry , catalysis , alkyne , selectivity , ligand (biochemistry) , reactivity (psychology) , chelation , palladium , combinatorial chemistry , conjugated system , medicinal chemistry , organic chemistry , receptor , biochemistry , polymer , medicine , alternative medicine , pathology
Palladium(II) complexes with a ligand set made from a chelating N‐heterocyclic dicarbene ligand and two weakly coordinating anions (generally introduced in situ upon addition of 2 equiv. of a suitable silver salt) were found to be very active and selective catalysts for the room‐temperature hydroarylation of alkynes at low catalyst loading (0.1 mol‐%). Moreover, the screening of various strong acids as reaction promoters revealed that both the strength of the acid and the coordinating ability of its conjugated base influence the catalytic performance. Most remarkably, the use of HBF 4 together with a dicarbene Pd complex catalyst provides a dramatic change in the selectivity of the reaction, with the prevalent formation of a product stemming from the insertion of two molecules of alkyne into the aromatic C–H bond. The results presented herein highlight the fact that the dicarbene ligand, apart from stabilising the catalyst, is also able to enhance catalytic activity and, most notably, to steer the reaction selectivity towards novel products. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)