Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA BCH 4305, 1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa.
Angew Chem Int Ed Engl. 2014 Mar 10;53(11):3001-5. doi: 10.1002/anie.201311009. Epub 2014 Feb 12.
The selective functionalization of carbon-carbon σ bonds is a synthetic strategy that offers uncommon retrosynthetic disconnections. Despite progress in C-C activation and its great importance, the development of asymmetric reactions lags behind. Rhodium(I)-catalyzed selective oxidative additions into enantiotopic C-C bonds in cyclobutanones are reported. Even operating at a reaction temperature of 130 °C, the process is characterized by outstanding enantioselectivity with the e.r. generally greater than 99.5:0.5. The intermediate rhodacycle is shown to react with a wide variety of tethered olefins to deliver complex bicyclic ketones in high yields.
碳-碳σ键的选择性功能化是一种提供非经典逆合成切断的合成策略。尽管 C-C 活化取得了进展，并且具有重要意义，但不对称反应的发展仍然滞后。本文报道了铑（I）催化的环丁酮中对映异位 C-C 键的选择性氧化加成反应。即使在 130°C 的反应温度下，该过程也具有出色的对映选择性，ee 值通常大于 99.5:0.5。实验结果表明，中间体铑环可以与各种连接的烯烃反应，以高产率得到复杂的双环酮。
