Kekule-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard Domagk Str. 1, 53121 Bonn, Germany.
J Am Chem Soc. 2009 Nov 25;131(46):16989-99. doi: 10.1021/ja907817y.
In a combined theoretical and experimental study, an efficient catalytic reaction featuring epoxide opening and tetrahydrofuran formation through homolytic substitution reactions at C-O and Ti-O bonds was devised. The performance of these two key steps of the catalytic cycle was studied and could be adjusted by modifying the electronic properties of the catalysts through introduction of electron-donating or -withdrawing substituents to the titanocene catalysts. By regarding both steps as single electron versions of oxidative addition and reductive elimination, a mechanism-based platform for the design of catalysts and reagents for electron transfer reactions evolved that opens broad perspectives for further investigations.
在一项理论与实验相结合的研究中，设计了一种通过 C-O 和 Ti-O 键的均裂取代反应实现环氧化物开环和四氢呋喃形成的高效催化反应。通过向钛茂催化剂中引入供电子或吸电子取代基来修饰催化剂的电子性质，可以研究和调节催化循环中这两个关键步骤的性能。通过将这两个步骤视为氧化加成和还原消除的单电子版本，为电子转移反应的催化剂和试剂设计建立了一个基于机理的平台，为进一步的研究开辟了广阔的前景。
