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

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Stereochemistry of the Kabachnik-Fields Condensation of Terpenic Amino Oximes with Aldehydes and Dimethyl Phosphite. / Marenin, Konstantin S.; Agafontsev, Alexander M.; Bryleva, Yuliya A. et al.

In: ChemistrySelect, Vol. 5, No. 25, 07.07.2020, p. 7596-7604.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{e816350d00a4487d839e1d1751c7ce38,

title = "Stereochemistry of the Kabachnik-Fields Condensation of Terpenic Amino Oximes with Aldehydes and Dimethyl Phosphite",

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).",

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",

author = "Marenin, {Konstantin S.} and Agafontsev, {Alexander M.} and Bryleva, {Yuliya A.} and Gatilov, {Yuri V.} and Glinskaya, {Ludmila A.} and Piryazev, {Dmitry A.} and Tkachev, {Alexey V.}",

year = "2020",

month = jul,

day = "7",

doi = "10.1002/slct.202002369",

language = "English",

volume = "5",

pages = "7596--7604",

journal = "ChemistrySelect",

issn = "2365-6549",

publisher = "Wiley-Blackwell",

number = "25",

}

RIS

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.

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