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

Title
Hydrogen-Bond-Assisted Controlled C-H Functionalization via Adaptive Recognition of a Purine Directing Group
Authors
Hyun Jin KimManjaly J. AjithaYongjae Lee류재윤Jin KimYunho LeeYousung JungSukbok Chang
Issue Date
2013-12
Publisher
Journal of the American Chemical Society
Citation
VOL 136, 1132-1140
Abstract
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.
URI
http://pubs.kist.re.kr/handle/201004/48554
ISSN
00027863
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