Metal-Catalyzed Isomerization of 5-Heteroatom-Substituted Isoxazoles­ as a New Route to 2-Halo-2H-azirines

Abstract

A convenient gram-scale method for the preparation of 2-halo-2H-azirine-2-carboxylic acid esters, thioesters and amides via metal-catalyzed isomerization of 5-heteroatom-substituted 4-haloisoxazoles is developed. The formation of the esters and amides is efficiently catalyzed by Rh₂(Piv)₄, while FeCl₂·4H₂O is the catalyst of choice for the synthesis of the thioesters. In addition, rhodium catalysis is successfully applied in the synthesis of azirine-2-carboxylates from non-halogenated 5-alkoxyisoxazoles.

Key words

azirines - isoxazoles - haloheterocycles - rhodium(II) carboxylates - iron(II) chloride - catalysis - isomerization

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