Have it both ways: α-Aminated ketones can be prepared by the titanium(III)-catalyzed reductive radical cyclization of iminonitriles. Depending on the position of the nitrile at the imine carbon or nitrogen, cyclic aminoketones or pyrrolidin-3-ones with a tetrasubstituted α-carbon can be formed in up to quantitative yield. In the latter case, the imine condensation and TiIII catalysis correspond to a formal [4+1] cycloaddition.
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