A meta-selective C-H borylation directed by a secondary interaction between ligand and substrate

Yoichiro Kuninobu, Haruka Ida, Mitsumi Nishi, Motomu Kanai

Research output: Contribution to journalArticle

180 Citations (Scopus)

Abstract

Regioselective C-H bond transformations are potentially the most efficient method for the synthesis of organic molecules. However, the presence of many C-H bonds in organic molecules and the high activation barrier for these reactions make these transformations difficult. Directing groups in the reaction substrate are often used to control regioselectivity, which has been especially successful for the ortho-selective functionalization of aromatic substrates. Here, we describe an iridium-catalysed meta-selective C-H borylation of aromatic compounds using a newly designed catalytic system. The bipyridine-derived ligand that binds iridium contains a pendant urea moiety. A secondary interaction between this urea and a hydrogen-bond acceptor in the substrate places the iridium in close proximity to the meta-C-H bond and thus controls the regioselectivity. 1 H NMR studies and control experiments support the participation of hydrogen bonds in inducing regioselectivity. Reversible direction of the catalyst through hydrogen bonds is a versatile concept for regioselective C-H transformations.

Original languageEnglish
Pages (from-to)712-717
Number of pages6
JournalNature Chemistry
Volume7
Issue number9
DOIs
Publication statusPublished - Sep 22 2015
Externally publishedYes

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Iridium
Regioselectivity
Hydrogen bonds
Ligands
Urea
Substrates
Molecules
Aromatic compounds
Chemical activation
Nuclear magnetic resonance
Catalysts
Experiments

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

A meta-selective C-H borylation directed by a secondary interaction between ligand and substrate. / Kuninobu, Yoichiro; Ida, Haruka; Nishi, Mitsumi; Kanai, Motomu.

In: Nature Chemistry, Vol. 7, No. 9, 22.09.2015, p. 712-717.

Research output: Contribution to journalArticle

Kuninobu, Yoichiro ; Ida, Haruka ; Nishi, Mitsumi ; Kanai, Motomu. / A meta-selective C-H borylation directed by a secondary interaction between ligand and substrate. In: Nature Chemistry. 2015 ; Vol. 7, No. 9. pp. 712-717.
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