Rh2(OAc)4-catalyzed reaction of α-diazocarbonyl compounds with 2-carbonyl-substituted 2H-azirines

K.V. Zavyalov, M.S. Novikov, A.F. Khlebnikov, D.S. Yufit

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14 Citations (Scopus)

Abstract

The Rh-2(OAc)(4)-catalyzed reaction of 2H-azirine-2-carbaldehydes with dimethyl diazomalonate proceeds via azirinium ylide formation, isomerization to 2-azabuta-1,3-dienes followed by 1,6-pi-electrocyclization to give 2H-1,3-oxazines. According to DFT-calculations ring opening of azirinium ylides should occur stereoselectively to give 2-azadienes with the C=C bond exclusively in the Z configuration. Changing a formyl group for an acetyl group in the azirine leads to a lowering of stereoselectivity and the formation of azadienes with an E configuration of the C=C bond was observed. The reaction of 2-acy1-2-diazoacetates with 2H-azirine-2-carbaldehydes proceeds similarly, but the 2-acetyl-substituted 2H-1,3-oxazines formed are unstable under chromatographic purification and rearrange easily into pyrrole derivatives. (C) 2013 Elsevier Ltd. All rights reserved.
Original languageEnglish
Pages (from-to)4546-4551
Number of pages6
JournalTetrahedron
Volume69
Issue number23
DOIs
Publication statusPublished - 2013

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