title: 4-Halo-2-azabuta-1,3-dienes as intermediates in the rhodium carbenoid-initiated transformation of 2-halo-2H-azirines into 2,3-dihydroazetes and 2,5-dihydrooxazoles
metadata.name: dc.contributor.author
metadata.value: Smetanin, Ilia A.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Novikov, Mikhail S.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Rostovskii, Nikolai V.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Khlebnikov, Alexander F.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Starova, Galina L.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Yufit, Dmitry S.
metadata.lang: -
metadata.name: dc.date.accessioned
metadata.value: 2016-04-07T21:44:43Z
metadata.lang: -
metadata.name: dc.date.available
metadata.value: 2016-04-07T21:44:43Z
metadata.lang: -
metadata.name: dc.date.issued
metadata.value: 2015-07
metadata.lang: -
metadata.name: dc.identifier.citation
metadata.value: Tetrahedron 71 (2015) 4616-4628
metadata.lang: en_GB
metadata.name: dc.identifier.issn
metadata.value: 0040-4020
metadata.lang: -
metadata.name: dc.identifier.uri
metadata.value: http://hdl.handle.net/11701/1962
metadata.lang: -
metadata.name: dc.description.abstract
metadata.value: A wide range of electron-poor 4-bromo-/4-chloro-2-azabuta-1,3-dienes were synthesized by the
  Rh2(OAc)4-catalyzed reaction of diazo esters and diazo ketones with methyl 2-halo-2H-azirine-2-
  carboxylates. The E stereoselectivity with respect to the configuration of the C]C bond of the 2-
  azadiene moiety is in good agreement with the results of DFT (M06-2X/6-31þG(d,p)) calculations of
  the reaction pathway. The reaction proceeds via the formation of an azirinium ylide intermediate followed
  by ring opening with outward rotation of the halogen atom. Depending on the substitution pattern at C1 electron-poor 4-halo-2-azabutadienes can undergo two types of cyclization at elevated temperatures: reversible 1,4-electrocyclization to give 2,3-dihydroazetes or 1,5-exo-trig cyclization to give 5-methylene-2,5-dihydrooxazoles, both in good yields. The dihydrooxazole derivatives can be also obtained at ambient temperature under DBU catalysis.
metadata.lang: en_GB
metadata.name: dc.language.iso
metadata.value: en
metadata.lang: en_GB
metadata.name: dc.publisher
metadata.value: Elsevier
metadata.lang: en_GB
metadata.name: dc.relation.ispartofseries
metadata.value: Tetrahedron;Vol. 71
metadata.lang: -
metadata.name: dc.subject
metadata.value: 2-Azabutadienes
metadata.lang: en_GB
metadata.name: dc.subject
metadata.value: Azirines
metadata.lang: en_GB
metadata.name: dc.subject
metadata.value: Diazo compounds
metadata.lang: en_GB
metadata.name: dc.subject
metadata.value: 2,3-Dihydroazetes
metadata.lang: en_GB
metadata.name: dc.subject
metadata.value: 2,5-Dihydrooxazoles
metadata.lang: en_GB
metadata.name: dc.subject
metadata.value: Heterocyclizations
metadata.lang: en_GB
metadata.name: dc.title
metadata.value: 4-Halo-2-azabuta-1,3-dienes as intermediates in the rhodium carbenoid-initiated transformation of 2-halo-2H-azirines into 2,3-dihydroazetes and 2,5-dihydrooxazoles
metadata.lang: en_GB
metadata.name: dc.type
metadata.value: Article
metadata.lang: en_GB
resources.filename: grafical abstract3.png
resources.url: https://dspace.spbu.ru/bitstream/11701/1962/1/grafical%20abstract3.png
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