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The Gold‐Catalyzed Hydroarylation of Alkynes with Electron‐Rich Heteroarenes – A Kinetic Investigation and New Synthetic Possibilities
Author(s) -
Schießl Jasmin,
Rudolph Matthias,
Hashmi A. Stephen K.
Publication year - 2017
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201600940
Subject(s) - chemistry , alkyne , reactivity (psychology) , acetylide , catalysis , adduct , kinetic energy , combinatorial chemistry , photochemistry , medicinal chemistry , organic chemistry , medicine , physics , alternative medicine , pathology , quantum mechanics
The gold‐catalyzed mono‐hydroarylation and two‐fold hydroarylation of alkynes with electron‐rich heteroarenes was analyzed by a 1 H NMR kinetic study. The obtained rate constants for the decreasing alkyne concentration provide information on the reactivity of this addition reaction. The examinations show the orthogonal reactivity of gold and a proton for the two reaction steps. The first hydroarylation is exclusively promoted by gold(I), whereas the second step is premised on a proton which will be reversibly derived from the formation of σ,π‐acetylide complexes from the terminal alkynes or by interaction with solvents. Based on kinetic data, it was possible to synthesize a large range of mono‐adducts in moderate to good yields, furthermore the synthesis of hetero‐di‐adducts, bearing two different substituents, was explored.