Atom-efficient regioselective 1,2-dearomatization of functionalized pyridines by an earth-abundant organolanthanide catalyst

Alexander S. Dudnik, Victoria L. Weidner, Alessandro Motta, Massimiliano Delferro, Tobin J Marks

Research output: Contribution to journalArticle

81 Citations (Scopus)

Abstract

Developing earth-abundant, non-platinum metal catalysts for high-value chemical transformations is a critical challenge to contemporary chemical synthesis. Dearomatization of pyridine derivatives is an important transformation to access a wide range of valuable nitrogenous natural products, pharmaceuticals and materials. Here, we report an efficient 1,2-regioselective organolanthanide-catalysed pyridine dearomatization process using pinacolborane, which is compatible with a broad range of pyridines and functional groups and employs equimolar reagent stoichiometry. Regarding the mechanism, derivation of the rate law from NMR spectroscopic and kinetic measurements suggests first order in catalyst concentration, fractional order in pyridine concentration and inverse first order in pinacolborane concentration, with C=N insertion into the La-H bond as turnover-determining. An energetic span analysis affords a more detailed understanding of experimental activity trends and the unusual kinetic behaviour, and proposes the catalystresting state and potential deactivation pathways.

Original languageEnglish
Pages (from-to)1100-1107
Number of pages8
JournalNature Chemistry
Volume6
Issue number12
DOIs
Publication statusPublished - 2014

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Pyridines
Pyridine
Earth (planet)
Atoms
Catalysts
Kinetics
Biological Products
Stoichiometry
Functional groups
Metals
Nuclear magnetic resonance
Drug products
Derivatives
Pharmaceutical Preparations
pyridine
4,4,5,5-tetramethyl(1,3,2)dioxaborolane

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Atom-efficient regioselective 1,2-dearomatization of functionalized pyridines by an earth-abundant organolanthanide catalyst. / Dudnik, Alexander S.; Weidner, Victoria L.; Motta, Alessandro; Delferro, Massimiliano; Marks, Tobin J.

In: Nature Chemistry, Vol. 6, No. 12, 2014, p. 1100-1107.

Research output: Contribution to journalArticle

Dudnik, Alexander S. ; Weidner, Victoria L. ; Motta, Alessandro ; Delferro, Massimiliano ; Marks, Tobin J. / Atom-efficient regioselective 1,2-dearomatization of functionalized pyridines by an earth-abundant organolanthanide catalyst. In: Nature Chemistry. 2014 ; Vol. 6, No. 12. pp. 1100-1107.
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