CpRu]‐Catalyzed Carbene Insertions into Epoxides: 1,4‐Dioxene Synthesis through SN1‐Like Chemistry with Retention of Configuration

Abstract

AbstractRather than lead to the usual deoxygenation pathway, metal carbenes derived from α‐diazo‐β‐ketoesters undergo three‐atom insertions into epoxides using a combination of 1,10‐phenanthroline and [CpRu(CH3CN)3][BArF] as the catalyst. Original 1,4‐dioxene motifs are obtained as single regio‐ and stereoisomers. A perfect syn stereochemistry (retention, e.r. up to 97:3) is observed for the ring opening, which behaves as an SN1‐like transformation.