Institute of Organic Chemistry, University of Paderborn, Warburger Strasse 100, 33098, Paderborn, Germany.
Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, University of Bonn, Beringstrasse 4, 53115, Bonn, Germany.
Angew Chem Int Ed Engl. 2016 Mar 18;55(13):4336-9. doi: 10.1002/anie.201511921. Epub 2016 Mar 3.
The first frustrated Lewis pair-catalyzed cycloisomerization of a series of 1,5-enynes was developed. The reaction proceeds via the π-activation of the alkyne and subsequent 5-endo-dig cyclization with the adjacent alkene. The presence of PPh3 was of utmost importance on the one hand to prevent side reactions (for example, 1,1-carboboration) and on the other hand for the efficient protodeborylation to achieve the catalytic turnover. The mechanism is explained on the basis of quantum-chemical calculations, which are in full agreement with the experimental observations.
首次开发了一系列 1,5-烯炔的受阻路易斯对催化环异构化反应。该反应通过炔烃的π-活化和相邻烯烃的后续 5-endo-dig 环化进行。三苯基膦 (PPh3) 的存在一方面极为重要，可以防止副反应（例如 1,1-碳硼化），另一方面可以有效地进行原脱硼化以实现催化周转。该机理是基于量子化学计算来解释的，与实验观察结果完全一致。
