Gansäuer A, Hildebrandt S, Vogelsang E, Flowers Ii R A
Kekulé-Instiut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.
Department of Chemistry, Lehigh University, Bethlehem, PA 18015, USA.
Dalton Trans. 2016 Jan 14;45(2):448-52. doi: 10.1039/c5dt03891j.
Radical-based transformations are an attractive target for the development of catalytic processes due to ease of radical generation, high functional group tolerance and selectivity of bond-forming reactions. In spite of these appealing features, the potential of radicals as key intermediates in catalysis remains largely untapped. Herein we present recent work that exploits the innate ability of titanocene-based catalysts to undergo both oxidative addition and reductive elimination in single electron steps. We further demonstrate that tuning the redox properties of the titanocene-based catalyst can be used to develop efficient catalytic free radical processes including tetrahydrofuran synthesis, and radical arylation.
基于自由基的转化反应因其易于产生自由基、对官能团具有高耐受性以及成键反应的选择性，而成为催化过程开发中一个具有吸引力的目标。尽管具有这些吸引人的特性，但自由基作为催化关键中间体的潜力在很大程度上仍未得到开发。在此，我们展示了近期的工作，该工作利用了基于二茂钛的催化剂在单电子步骤中既能进行氧化加成又能进行还原消除的固有能力。我们进一步证明，调节基于二茂钛的催化剂的氧化还原性质可用于开发高效的催化自由基过程，包括四氢呋喃的合成以及自由基芳基化反应。
