Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen (Germany).
Angew Chem Int Ed Engl. 2014 Jul 21;53(30):7760-4. doi: 10.1002/anie.201402557. Epub 2014 Jun 12.
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 C-CAu 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.
金（I）催化的氢胺化的实验机理研究表明，构象柔性的金-亚胺盐 Au-Im 的形成源于乙烯基金物种的质子化。C-CAu 键的旋转是原脱金立体特异性丧失的原因，这解释了 Stradiotto 反应的立体化学结果。因此，关于内球或外球机理的模糊性得到了解决，有利于外球机理。
