A high-yielding method for the synthesis of 2H-1,3,5-oxadi-azines by rhodium(II)- or copper(II)-catalyzed reaction of 1,2,4-oxadi-azoles with α-diazo esters has been developed. The reaction proceeds via attack of the metallocarbenoid on the oxadiazole N2 atom followed by ring opening/1,6-electrocyclization and enables the introduction of alkyl, aryl, oxy, and amino substituents into the 6-position and electron-withdrawing groups into the 2-position of 1,3,5-oxadiazine. The N2-attack and the N4-attack of the carbenoid cause different oxadiazole ring openings, which are controlled by the substitution at C5. The presence of a substituent at this position is a prerequisite for the N2-attack to occur, leading to the formation of 1,3,5-oxadiazines.

Original languageEnglish
Article numberss-2020-n0194-op
JournalSynthesis (Germany)
Early online date29 Sep 2020
Publication statusE-pub ahead of print - 29 Sep 2020

Scopus subject areas

  • Catalysis
  • Organic Chemistry

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