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Review | Regular issue | Vol 89, No. 4, 2014, pp.845-868
Published online, 3rd February, 2014
DOI: 10.3987/REV-13-791
Heterocyclic Synthesis by π-Acidic Metal Catalyzed Reactions via N-O Bond Cleavage

Itaru Nakamura* and Masahiro Terada

*Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan


This review contains recent progress in heterocyclic synthesis by π-acidic metal catalyzed reactions via N-O bond cleavage. The reaction involving a terminal N-O bond (R3N+-O-) predominantly proceeds via nucleophilic attack of the O atom and subsequent formation of an α-oxo carbenoid intermediate through N-O bond cleavage. In contrast, the reaction of oximes and hydroxylamine derivatives having an internal N-O bond (R2N-OR’) is initiated by the nucleophilic attack of either N or O atom. In addition, hydroxylamine derivatives have been utilized as an external reagent in the cyclization reaction. The methodology produces a wide variety of highly functionalized nitrogen and oxygen heterocycles in an efficient manner under mild reaction conditions.