Tuning the redox properties of the titanocene(III)/(IV)-couple for atom-economical catalysis in single electron steps
Tuning the redox properties of the titanocene(III)/(IV)-couple for atom-economical catalysis in single electron steps
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DOI：
10.1039/c5dt03891j
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发表时间：
2016-01-01
影响因子：
4
通讯作者：
Flowers, R. A., II
中科院分区：
文献类型：
--
作者：
Gansaeuer, A.;Hildebrandt, S.;Flowers, R. A., II
基于自由基的转化由于易于自由基生成、高官能团耐受性和成键反应的选择性而成为催化过程开发的有吸引力的目标。尽管有这些吸引人的特征，自由基作为催化中关键中间体的潜力在很大程度上仍未开发。在此，我们提出了最近的工作，利用的固有能力，二茂钛基催化剂进行氧化加成和还原消除在单电子步骤。我们进一步证明，调整的二茂钛基催化剂的氧化还原性能，可用于开发有效的催化自由基过程，包括四氢呋喃合成，和自由基芳基化。
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.