A Direct Entry to Substituted N ‐Methoxyamines from N ‐Methoxyamides via N ‐Oxyiminium Ions

Take the direct path : Sequential nucleophilic addition of N ‐methoxyamides using DIBAL and organometallic reagents provided substituted N ‐methoxyamines in one pot via five‐membered chelated intermediates (see scheme, DIBAL=diisobutylaluminum hydride). The reaction allows functionalization of acyclic amides and macrolactams without a preactivation step, which is generally required for inert amide carbonyl groups.