Iodoarene-Catalyzed Stereospecific Intramolecular sp3 C鈥揌 Amination: Reaction Development and Mechanistic Insights
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- 作者：Chendan Zhu ; Yong Liang ; Xin Hong ; Heqing Sun ; Wei-Yin Sun ; K. N. Houk ; Zhuangzhi Shi
- 刊名：Journal of the American Chemical Society
- 出版年：2015
- 出版时间：June 24, 2015
- 年：2015
- 卷：137
- 期：24
- 页码：7564-7567
- 全文大小：410K
- ISSN：1520-5126
文摘
A new strategy is reported for intramolecular sp3 C鈥揌 amination under mild reaction conditions using iodoarene as catalyst and m-CPBA as oxidant. This C鈥揌 functionalization involving iodine(III) reagents generated in situ occurs readily at sterically hindered tertiary C鈥揌 bonds. DFT (M06-2X) calculations show that the preferred pathway involves an iodonium cation intermediate and proceeds via an energetically concerted transition state, through hydride transfer followed by the spontaneous C鈥揘 bond formation. This leads to the experimentally observed amination at a chiral center without loss of stereochemical information.