Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirinering expansion: Dedicated to Professor Armin de Meijere on the occasion of his 75th birthday

Kirill V. Zavyalov, Mikail S. Novikov, Alexander F. Khlebnikov, Viktoriia V. Pakalnis

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17 Citations (Scopus)

Abstract

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative. © 2014 Elsevier Ltd. All rights reserved.
Original languageEnglish
Pages (from-to)3377-3384
Number of pages8
JournalTetrahedron
Volume70
Issue number21
DOIs
Publication statusPublished - 2014

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Armin
Oxazines
Azirines
Pyrroles
Temperature
Cyclization
Discrete Fourier transforms
Derivatives
Atoms
Kinetics
oxazine 1

Cite this

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title = "Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirinering expansion: Dedicated to Professor Armin de Meijere on the occasion of his 75th birthday",
abstract = "The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative. {\circledC} 2014 Elsevier Ltd. All rights reserved.",
author = "Zavyalov, {Kirill V.} and Novikov, {Mikail S.} and Khlebnikov, {Alexander F.} and Pakalnis, {Viktoriia V.}",
year = "2014",
doi = "10.1016/j.tet.2014.03.101",
language = "English",
volume = "70",
pages = "3377--3384",
journal = "Tetrahedron",
issn = "0040-4020",
publisher = "Elsevier",
number = "21",

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T1 - Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirinering expansion

T2 - Dedicated to Professor Armin de Meijere on the occasion of his 75th birthday

AU - Zavyalov, Kirill V.

AU - Novikov, Mikail S.

AU - Khlebnikov, Alexander F.

AU - Pakalnis, Viktoriia V.

PY - 2014

Y1 - 2014

N2 - The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative. © 2014 Elsevier Ltd. All rights reserved.

AB - The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative. © 2014 Elsevier Ltd. All rights reserved.

U2 - 10.1016/j.tet.2014.03.101

DO - 10.1016/j.tet.2014.03.101

M3 - Article

VL - 70

SP - 3377

EP - 3384

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 21

ER -