Synthesis of 1,2-Dihydropyrimidine-2-carboxylates via Regioselective Addition of Rhodium(II) Carbenoids to 2H-Azirine-2-carbaldimines

Mikhail S. Novikov, Nikolai V. Rostovskii, Alexander N. Koronatov, Kirill V. Zavyalov, Grigory V. Zubakin, Alexander F. Khlebnikov, Galina L. Starova

Research output

9 Citations (Scopus)

Abstract

An efficient two-step procedure "imine formation/azirine-carbenoid coupling" has been developed for the preparation of 1,2-dihydropyrimidines from azirine-2-carbaldehydes, primary amines, and diazo carbonyl compounds under Rh(II) catalysis. The formation of 1,2-dihydropyrimidines involves 100% regioselective addition of the rhodium carbenoid to endocyclic nitrogen atom of the 2H-azirine-2-carbaldimine. According to the DFT calculations the reaction proceeds via dissociation of the metal-bound complex of the azirinium ylide to metal-free azirinium ylide, ring-opening of the latter to give a 1,5-diazahexa-1,3,5-triene, followed by 1,6-cyclization. The 1,2-dihydropyrimidines with two different electron-withdrawing substituents at the C2 position can undergo in solution inversion of configuration of the stereogenic center at C2 via "the N1-C2 bond cleavage/rotation around the N-C single bond/1,6-cyclization" sequence.

Original languageEnglish
Pages (from-to)13396-13404
Number of pages9
JournalJournal of Organic Chemistry
Volume82
Issue number24
DOIs
Publication statusPublished - 15 Dec 2017
Externally publishedYes

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Rhodium
Cyclization
Metals
Carbonyl compounds
Imines
Discrete Fourier transforms
Catalysis
Amines
Nitrogen
Atoms
Electrons
single bond

Scopus subject areas

  • Organic Chemistry

Cite this

@article{4d394c8ad5d9499ca6e884dc13ac6e08,
title = "Synthesis of 1,2-Dihydropyrimidine-2-carboxylates via Regioselective Addition of Rhodium(II) Carbenoids to 2H-Azirine-2-carbaldimines",
abstract = "An efficient two-step procedure {"}imine formation/azirine-carbenoid coupling{"} has been developed for the preparation of 1,2-dihydropyrimidines from azirine-2-carbaldehydes, primary amines, and diazo carbonyl compounds under Rh(II) catalysis. The formation of 1,2-dihydropyrimidines involves 100{\%} regioselective addition of the rhodium carbenoid to endocyclic nitrogen atom of the 2H-azirine-2-carbaldimine. According to the DFT calculations the reaction proceeds via dissociation of the metal-bound complex of the azirinium ylide to metal-free azirinium ylide, ring-opening of the latter to give a 1,5-diazahexa-1,3,5-triene, followed by 1,6-cyclization. The 1,2-dihydropyrimidines with two different electron-withdrawing substituents at the C2 position can undergo in solution inversion of configuration of the stereogenic center at C2 via {"}the N1-C2 bond cleavage/rotation around the N-C single bond/1,6-cyclization{"} sequence.",
author = "Novikov, {Mikhail S.} and Rostovskii, {Nikolai V.} and Koronatov, {Alexander N.} and Zavyalov, {Kirill V.} and Zubakin, {Grigory V.} and Khlebnikov, {Alexander F.} and Starova, {Galina L.}",
year = "2017",
month = "12",
day = "15",
doi = "10.1021/acs.joc.7b02484",
language = "English",
volume = "82",
pages = "13396--13404",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "24",

}

TY - JOUR

T1 - Synthesis of 1,2-Dihydropyrimidine-2-carboxylates via Regioselective Addition of Rhodium(II) Carbenoids to 2H-Azirine-2-carbaldimines

AU - Novikov, Mikhail S.

AU - Rostovskii, Nikolai V.

AU - Koronatov, Alexander N.

AU - Zavyalov, Kirill V.

AU - Zubakin, Grigory V.

AU - Khlebnikov, Alexander F.

AU - Starova, Galina L.

PY - 2017/12/15

Y1 - 2017/12/15

N2 - An efficient two-step procedure "imine formation/azirine-carbenoid coupling" has been developed for the preparation of 1,2-dihydropyrimidines from azirine-2-carbaldehydes, primary amines, and diazo carbonyl compounds under Rh(II) catalysis. The formation of 1,2-dihydropyrimidines involves 100% regioselective addition of the rhodium carbenoid to endocyclic nitrogen atom of the 2H-azirine-2-carbaldimine. According to the DFT calculations the reaction proceeds via dissociation of the metal-bound complex of the azirinium ylide to metal-free azirinium ylide, ring-opening of the latter to give a 1,5-diazahexa-1,3,5-triene, followed by 1,6-cyclization. The 1,2-dihydropyrimidines with two different electron-withdrawing substituents at the C2 position can undergo in solution inversion of configuration of the stereogenic center at C2 via "the N1-C2 bond cleavage/rotation around the N-C single bond/1,6-cyclization" sequence.

AB - An efficient two-step procedure "imine formation/azirine-carbenoid coupling" has been developed for the preparation of 1,2-dihydropyrimidines from azirine-2-carbaldehydes, primary amines, and diazo carbonyl compounds under Rh(II) catalysis. The formation of 1,2-dihydropyrimidines involves 100% regioselective addition of the rhodium carbenoid to endocyclic nitrogen atom of the 2H-azirine-2-carbaldimine. According to the DFT calculations the reaction proceeds via dissociation of the metal-bound complex of the azirinium ylide to metal-free azirinium ylide, ring-opening of the latter to give a 1,5-diazahexa-1,3,5-triene, followed by 1,6-cyclization. The 1,2-dihydropyrimidines with two different electron-withdrawing substituents at the C2 position can undergo in solution inversion of configuration of the stereogenic center at C2 via "the N1-C2 bond cleavage/rotation around the N-C single bond/1,6-cyclization" sequence.

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