Rh2(OAc)4-catalyzed reaction of 2-(2-carbonylvinyl)-3-phenyl-2H-azirines with diazo esters

K. V. Zavyalov, M. S. Novikov, F. Khlebnikov, N. V. Rostovskii, G. L. Starova

Research output

3 Citations (Scopus)

Abstract

Rh2(OAc)4-catalyzed reaction of 2-(2-carbonylvinyl)-3-phenyl-2H-azirines with diazo esters proceeds through an intermediate generation of azirinium ylide suffering a nonstereoselective ring opening to form (3Z)- and (3E)-2-azahexa-1,3,5-trienes. The former depending on configuration of the C5=C6 bond may undergo cyclization either in derivative of 2,3-dihydropyridine, or in pyrrolium ylide that isomerizes into a derivative of 1H-pyrrole. According to DFT calculation, the preferred formation of pyrroles at increasing volume of Z-substituent at the atom C6 and of substituents at the atom C1 of 2-azahexatriene occurs due to the destabilization of more sterically loaded transition states of 1,6-cyclization.

Original languageEnglish
Pages (from-to)1214-1221
Number of pages8
JournalRussian Journal of Organic Chemistry
Volume53
Issue number8
DOIs
Publication statusPublished - 2017
Externally publishedYes

Fingerprint

Azirines
Pyrroles
Cyclization
Esters
Derivatives
Atoms
Discrete Fourier transforms
dirhodium tetraacetate

Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Rh2(OAc)4-catalyzed reaction of 2-(2-carbonylvinyl)-3-phenyl-2H-azirines with diazo esters",
abstract = "Rh2(OAc)4-catalyzed reaction of 2-(2-carbonylvinyl)-3-phenyl-2H-azirines with diazo esters proceeds through an intermediate generation of azirinium ylide suffering a nonstereoselective ring opening to form (3Z)- and (3E)-2-azahexa-1,3,5-trienes. The former depending on configuration of the C5=C6 bond may undergo cyclization either in derivative of 2,3-dihydropyridine, or in pyrrolium ylide that isomerizes into a derivative of 1H-pyrrole. According to DFT calculation, the preferred formation of pyrroles at increasing volume of Z-substituent at the atom C6 and of substituents at the atom C1 of 2-azahexatriene occurs due to the destabilization of more sterically loaded transition states of 1,6-cyclization.",
author = "Zavyalov, {K. V.} and Novikov, {M. S.} and F. Khlebnikov and Rostovskii, {N. V.} and Starova, {G. L.}",
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T1 - Rh2(OAc)4-catalyzed reaction of 2-(2-carbonylvinyl)-3-phenyl-2H-azirines with diazo esters

AU - Zavyalov, K. V.

AU - Novikov, M. S.

AU - Khlebnikov, F.

AU - Rostovskii, N. V.

AU - Starova, G. L.

PY - 2017

Y1 - 2017

N2 - Rh2(OAc)4-catalyzed reaction of 2-(2-carbonylvinyl)-3-phenyl-2H-azirines with diazo esters proceeds through an intermediate generation of azirinium ylide suffering a nonstereoselective ring opening to form (3Z)- and (3E)-2-azahexa-1,3,5-trienes. The former depending on configuration of the C5=C6 bond may undergo cyclization either in derivative of 2,3-dihydropyridine, or in pyrrolium ylide that isomerizes into a derivative of 1H-pyrrole. According to DFT calculation, the preferred formation of pyrroles at increasing volume of Z-substituent at the atom C6 and of substituents at the atom C1 of 2-azahexatriene occurs due to the destabilization of more sterically loaded transition states of 1,6-cyclization.

AB - Rh2(OAc)4-catalyzed reaction of 2-(2-carbonylvinyl)-3-phenyl-2H-azirines with diazo esters proceeds through an intermediate generation of azirinium ylide suffering a nonstereoselective ring opening to form (3Z)- and (3E)-2-azahexa-1,3,5-trienes. The former depending on configuration of the C5=C6 bond may undergo cyclization either in derivative of 2,3-dihydropyridine, or in pyrrolium ylide that isomerizes into a derivative of 1H-pyrrole. According to DFT calculation, the preferred formation of pyrroles at increasing volume of Z-substituent at the atom C6 and of substituents at the atom C1 of 2-azahexatriene occurs due to the destabilization of more sterically loaded transition states of 1,6-cyclization.

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