Hydrogen-bond-assisted controlled C-H functionalization via adaptive recognition of a purine directing group

Hyun Jin Kim, Manjaly J. Ajitha, Yongjae Lee, Jaeyune Ryu, Jin Kim, Yunho Lee, Yousung Jung*, Sukbok Chang

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

137 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)1132-1140
Number of pages9
JournalJournal of the American Chemical Society
Volume136
Issue number3
DOIs
StatePublished - Jan 22 2014

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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