Hydrogen-Bond-Assisted Controlled C–H Functionalization via Adaptive Recognition of a Purine Directing Group

详细信息    查看全文

• 作者：Hyun Jin Kim ; Manjaly J. Ajitha ; Yongjae Lee ; Jaeyune Ryu ; Jin Kim ; Yunho Lee ; Yousung Jung ; Sukbok Chang
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：January 22, 2014
• 年：2014
• 卷：136
• 期：3
• 页码：1132-1140
• 全文大小：596K
• ISSN：1520-5126

文摘

We have developed the Rh-catalyzed selective C鈥揌 functionalization of 6-arylpurines, in which the purine moiety directs the C鈥揌 bond activation of the aryl pendant. While the first C鈥揌 amination proceeds via the N1-chelation assistance, the subsequent second C鈥揌 bond activation takes advantage of an intramolecular hydrogen-bonding interaction between the initially formed amino group and one nitrogen atom, either N1 or N7, of the purinyl part. Isolation of a rhodacycle intermediate and the substrate variation studies suggest that N1 is the main active site for the C鈥揌 functionalization of both the first and second amination in 6-arylpurines, while N7 plays an essential role in controlling the degree of functionalization serving as an intramolecular hydrogen-bonding site in the second amination process. This pseudo-Curtin鈥揌ammett situation was supported by density functional calculations, which suggest that the intramolecular hydrogen-bonding capability helps second amination by reducing the steric repulsion between the first installed ArNH and the directing group.