Interrupted Dance of Five Heteroatoms: Reinventing Ozonolysis to Make Geminal Alkoxyhydroperoxides from C═N Bonds

2024/04/02 by Ivan A. Yaremenko, Dmitri I. Fomenkov, Roman A. Budekhin +7 · 2 citations
Chemistry · #Chemical Reactions and Mechanisms #Oxidative Organic Chemistry Reactions #Asymmetric Synthesis and Catalysis

paper · doi:10.1021/acs.joc.4c00233

Abstract

Four heteroatoms dance in the cascade of four pericyclic reactions initiated by ozonolysis of C═N bonds. Switching from imines to semicarbazones introduces the fifth heteroatom that slows this dance, delays reaching the thermodynamically favorable escape path, and allows efficient interception of carbonyl oxides (Criegee intermediates, CIs) by an external nucleophile. The new three-component reaction of alcohols, ozone, and oximes/semicarbazones greatly facilitates synthetic access to monoperoxyacetals (alkoxyhydroperoxides).

Citations

• Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint

Cited by

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