Transition-Metal-Free Self-Hydrogen-Transferring Allylic Isomerization
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- 作者：Hong-Xing Zheng ; Zu-Feng Xiao ; Chuan-Zhi Yao ; Qiang-Qiang Li ; Xiao-Shan Ning ; Yan-Biao Kang ; Yong Tang
- 刊名：Organic Letters
- 出版年：2015
- 出版时间：December 18, 2015
- 年：2015
- 卷：17
- 期：24
- 页码：6102-6105
- 全文大小：462K
- ISSN：1523-7052
文摘
Phenanthroline and tert-butoxide have been established as powerful radical initiators in reactions such as the SRN1-type coupling reactions due to the cooperation of large heteroarenes and a special feature of tert-butoxide. The first phenanthroline-tert-butoxide-catalyzed transition-metal-free allylic isomerization is described. The resulting ketones are key intermediates for indenes. The control experiments rule out the base-promoted allylic anion pathway. The radical pathway is supported by experimental evidence that includes kinetic study, kinetic isotope effect, isotope-labeling experiments, trapping experiments, and EPR experiments.