Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Stereochemistry of the Kabachnik-Fields Condensation of Terpenic Amino Oximes with Aldehydes and Dimethyl Phosphite. / Marenin, Konstantin S.; Agafontsev, Alexander M.; Bryleva, Yuliya A. и др.
в: ChemistrySelect, Том 5, № 25, 07.07.2020, стр. 7596-7604.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Stereochemistry of the Kabachnik-Fields Condensation of Terpenic Amino Oximes with Aldehydes and Dimethyl Phosphite
AU - Marenin, Konstantin S.
AU - Agafontsev, Alexander M.
AU - Bryleva, Yuliya A.
AU - Gatilov, Yuri V.
AU - Glinskaya, Ludmila A.
AU - Piryazev, Dmitry A.
AU - Tkachev, Alexey V.
N1 - Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Copyright: Copyright 2020 Elsevier B.V., All rights reserved.
PY - 2020/7/7
Y1 - 2020/7/7
N2 - 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).
AB - 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).
KW - carene
KW - DFT calculations
KW - Kabachnik-Fields reaction
KW - pinene
KW - spin-spin coupling
KW - ALPHA-AMINOPHOSPHONATE
KW - ONE-POT SYNTHESIS
KW - NONCOVALENT INTERACTIONS
KW - COUPLING-CONSTANTS
KW - DENSITY FUNCTIONALS
KW - FITTING BASIS-SETS
KW - BIOLOGICAL-ACTIVITY
KW - ORGANO-PHOSPHORUS COMPOUNDS
KW - M06 SUITE
KW - NITROSO CHLORIDES
UR - http://www.scopus.com/inward/record.url?scp=85087505119&partnerID=8YFLogxK
U2 - 10.1002/slct.202002369
DO - 10.1002/slct.202002369
M3 - Article
AN - SCOPUS:85087505119
VL - 5
SP - 7596
EP - 7604
JO - ChemistrySelect
JF - ChemistrySelect
SN - 2365-6549
IS - 25
ER -
ID: 24720208