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

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

Journal

ChemistrySelect
ISSN: 2365-6549

Output data

Year: 2020, Volume: 5, Number: 25, Pages: 7596-7604 Pages count : 9 DOI: 10.1002/slct.202002369

Tags

Kabachnik-Fields reaction; carene; pinene; DFT calculations; spin-spin coupling

Authors

Marenin Konstantin S. ¹ , Agafontsev Alexander M. ¹ , Bryleva Yuliya A. ^2,3 , Gatilov Yuri V. ¹ , Glinskaya Ludmila A. ² , Piryazev Dmitry A. ² , Tkachev Alexey V. ¹

Affiliations

1	(Данные Web of science) Russian Acad Sci, NN Vorozhtsov Novosibirsk Inst Organ Chem, Siberian Branch, 9 Academician Lavrentiev Ave, Novosibirsk 630090, Russia
2	(Данные Web of science) Russian Acad Sci, Nikolaev Inst Inorgan Chem, Siberian Branch, 3 Academician Lavrentiev Ave, Novosibirsk 630090, Russia
3	(Данные Web of science) Novosibirsk State Univ, Dept Nat Sci, 2 Pirogiva Str, Novosibirsk 630090, Russia

Three-component condensation of aldehydes and dimethyl phosphite with alpha-amino oximes derived from (-)-alpha-pinene and (+)-3-carene (Kabachnik-Fields reaction) resulted in amino phosphonates as pairs of diastereomers. Diastereomeric ratio depends on the catalyst used (SnCl(2)x2H(2)O, 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 alpha-amino phosphonates should be conformationally inhomogeneous, exhibiting a tendency to form H-bonded dimers (DFT M06/def2-SVP, IR). One-bond spin-spin coupling(1)J(P-C)was found to be diagnostic for the configuration assignment since the value(1)J(P-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).

Marenin K.S. , Agafontsev A.M. , Bryleva Y.A. , Gatilov Y.V. , Glinskaya L.A. , Piryazev D.A. , Tkachev A.V.
Stereochemistry of the Kabachnik-Fields Condensation of Terpenic Amino Oximes with Aldehydes and Dimethyl Phosphite
ChemistrySelect. 2020. V.5. N25. P.7596-7604. DOI: 10.1002/slct.202002369 WOS Scopus РИНЦ OpenAlex

Published online:	Jul 3, 2020
Published print:	Jul 7, 2020

Web of science:	WOS:000545756700037
Scopus:	2-s2.0-85087505119
Elibrary:	45446822
OpenAlex:	W3039039872

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