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Cyclopropenium-activated Beckmann rearrangement. Catalysis versus self-propagation in reported organocatalytic Beckmann rearrangements

2010; Royal Society of Chemistry; Volume: 1; Issue: 6 Linguagem: Inglês

10.1039/c0sc00421a

2041-6539

Christine M. Vanos, Tristan H. Lambert,

Ferrocene Chemistry and Applications

The concept of cyclopropenium activation has been extended to include dehydrative rearrangements in the context of the Beckmann rearrangement. Geminal dichlorocyclopropenes are shown to rapidly and efficiently convert oximes to amides at room temperature, with reactivity that far surpasses other organic-based promoters. Twelve total examples are provided, including a complex steroidal substrate on preparative scale. Evidence is provided that suggests previously reported organocatalytic Beckmann rearrangements may in fact be self-propagating rather than catalytic.