Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Spain.
Org Biomol Chem. 2012 Aug 14;10(30):6105-11. doi: 10.1039/c2ob25419k. Epub 2012 May 31.
1,6-Enynes with electron-donating substituents at the alkyne undergo gold(I)-catalysed single cleavage skeletal rearrangement, whereas substrates with electron-withdrawing substituents evolve selectively to double cleavage rearrangement. Theoretical calculations provide a qualitative rationale for these effects, and suggest that bicyclo[3.2.0]hept-5-enes are involved as intermediates. We provide the first X-ray structural evidence for the formation of a product of this class in a cycloisomerisation of a 1,6-enyne.
带有供电子取代基的 1,6-烯炔经金（I）催化发生单断裂骨架重排，而带有吸电子取代基的底物则选择性地进行双断裂重排。理论计算为这些效应提供了定性的原理，并表明双环[3.2.0]庚-5-烯作为中间体参与其中。我们首次提供了 X 射线结构证据，证明在 1,6-烯炔的环异构化中形成了此类产物。
