Institute of Chemical Research of Catalonia (ICIQ), Av. Pasos Catalans 16, 43007 Tarragona, Spain.
Chemistry. 2011 Sep 19;17(39):10972-8. doi: 10.1002/chem.201101749.
The carbene or carbocationic nature of the intermediates in the gold-catalyzed cycloisomerization of 1,5-enynes can be revealed, depending on the ligands on the gold catalysts. Gold complexes with highly electron-donating ligands promote reactions that proceed via intermediates with carbene-like character, leading to products with a bicyclo[3.1.0]hexene skeleton. The intermediate cyclopropyl endo-gold carbenes formed in this cyclization have been trapped, for the first time, to give biscyclopropane derivatives in a reaction that proceeds in a concerted fashion, according to DFT calculations.
金催化的 1,5-烯炔环异构化反应中中间体的卡宾或碳阳离子性质可以根据金催化剂上的配体来揭示。具有强给电子配体的金配合物促进通过具有类似卡宾特征的中间体进行的反应，导致具有双环[3.1.0]己烯骨架的产物。在这个环化反应中形成的中间体环丙基内-金卡宾首次被捕获，根据 DFT 计算，以协同方式进行反应，得到双环丙烷衍生物。
