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Mechanistic Study of Gold(I)‐Catalyzed Hydroamination of Alkynes: Outer or Inner Sphere Mechanism?
Author(s) -
Zhdanko Alexander,
Maier Martin E.
Publication year - 2014
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.201402557
Subject(s) - hydroamination , iminium , protonation , chemistry , stereospecificity , mechanism (biology) , inner sphere electron transfer , catalysis , outer sphere electron transfer , reaction mechanism , stereochemistry , organic chemistry , physics , ion , quantum mechanics
An experimental mechanistic study of the gold(I)‐catalyzed hydroamination shows the formation of conformationally flexible auro‐iminium salts Au‐Im , which originate from the protonation of a vinyl gold species. Rotation around the CCAu bond is the reason for the loss of stereospecificity of protodeauration, which explains the stereochemical result of the Stradiotto reaction. The ambiguity about inner or outer sphere mechanism is thus resolved in favor of the outer sphere mechanism.