Seiser Tobias, Cramer Nicolai
Laboratorium für Organische Chemie, ETH Zürich.
Chimia (Aarau). 2010;64(3):153-6. doi: 10.2533/chimia.2010.153.
The catalytic activation of carbon-carbon single bonds represents a major challenge in organometallic chemistry. Strained ring substrates occupy in this respect a privileged role as their inherent ring strain facilitates the desired metal insertion. Employing symmetrically substituted tert-cyclobutanols, an enantioselective rhodium(I)-catalyzed beta-carbon elimination creates alkyl-rhodium species bearing all-carbon quaternary stereogenic centers. Downstream reactions enable access to a wide range of synthetically versatile products such as substituted cyclohexenones, lactones and indanols with excellent enantioselectivities of up to 99% ee.
碳-碳单键的催化活化是有机金属化学中的一项重大挑战。在这方面，张力环底物具有特殊作用，因为其固有的环张力有助于实现所需的金属插入。使用对称取代的叔环丁醇，铑(I)催化的对映选择性β-碳消除反应生成带有全碳季碳立体中心的烷基铑物种。后续反应能够得到多种具有广泛合成用途的产物，如取代环己烯酮、内酯和茚醇，对映选择性高达99%ee。
