Stereochemistry of the Kabachnik-Fields Condensation of Terpenic Amino Oximes with Aldehydes and Dimethyl Phosphite

Konstantin S. Marenin, Alexander M. Agafontsev, Yuliya A. Bryleva, Yuri V. Gatilov, Ludmila A. Glinskaya, Dmitry A. Piryazev, Alexey V. Tkachev

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3 Citations (Scopus)

Abstract

Three-component condensation of aldehydes and dimethyl phosphite with α-amino oximes derived from (−)-α-pinene and (+)-3-carene (Kabachnik-Fields reaction) resulted in amino phosphonates as pairs of diastereomers. Diastereomeric ratio depends on the catalyst used (SnCl2×2H2O, SiO2, Al2O3-H+) and the heating type (conventional or microwave). The best results were achieved by MW irradiation with simultaneous cooling. Stereochemical assignment of the key derivatives was made by X-ray diffractometry. According to quantum chemical calculations (DFT PBE0/def2-TZVPP) and spectroscopic data, the terpenic α-amino phosphonates should be conformationally inhomogeneous, exhibiting a tendency to form H-bonded dimers (DFT M06/def2-SVP, IR). One-bond spin-spin coupling 1JP–C was found to be diagnostic for the configuration assignment since the value 1JP–C depends on the dihedral angle between bond C−P and axis of the electron lone pair at the neighboring nitrogen (NMR, DFT PBE0/aug-cc-pVTZ−J).

Original languageEnglish
Pages (from-to)7596-7604
Number of pages9
JournalChemistrySelect
Volume5
Issue number25
DOIs
Publication statusPublished - 7 Jul 2020

Keywords

  • carene
  • DFT calculations
  • Kabachnik-Fields reaction
  • pinene
  • spin-spin coupling
  • ALPHA-AMINOPHOSPHONATE
  • ONE-POT SYNTHESIS
  • NONCOVALENT INTERACTIONS
  • COUPLING-CONSTANTS
  • DENSITY FUNCTIONALS
  • FITTING BASIS-SETS
  • BIOLOGICAL-ACTIVITY
  • ORGANO-PHOSPHORUS COMPOUNDS
  • M06 SUITE
  • NITROSO CHLORIDES

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