Divergent Synthesis Of Alpha-Functionalized Amides Through Selective N-O/C-C Or N-O/C-C/C-N Cleavage Of Aza-Cyclobutanone Oxime Esters

Herein, a novel sequential ring opening reaction of aza-cyclobutanone oxime esters with isocyanides is described. The reaction proceeded smoothly under redox-neutral and mild conditions, leading to a divergent synthesis of alpha-cyanomethylaminoamides, alpha-acyloxyamides and alpha-acylaminoamides. In these transformations, a selective N-O/C-C or N-O/C-C/C-N cleavage was achieved only by changing the iron-catalyst system. Among them, a rare sequential N-O/C-C/C-N cleavage process with a classical Passerini or Ugi multicomponent reaction can be executed in a single step. To the best of our knowledge, this work creates a novel reaction mode of cycloketone oximes and provides new opportunities for reaction design.