Hydrogen-Bond-Assisted Controlled C-H Functionalization via Adaptive Recognition of a Purine Directing Group
- Hydrogen-Bond-Assisted Controlled C-H Functionalization via Adaptive Recognition of a Purine Directing Group
- Hyun Jin Kim; Manjaly J. Ajitha; Yongjae Lee; 류재윤; Jin Kim; Yunho Lee; Yousung Jung; Sukbok Chang
- Issue Date
- Journal of the American Chemical Society
- VOL 136, 1132-1140
- We have developed the Rh-catalyzed selective C−H functionalization of 6-arylpurines, in which the purine moiety directs the C−H bond activation of the aryl pendant. While the first C−H amination proceeds via the N1-chelation assistance, the subsequent second C−H 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−H 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−Hammett 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.
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