Metal‐Free Direct Synthesis of Secondary Amides and Nitriles Using <i>O</i>‐(2‐Pyrimidinyl)‐<i>N</i>‐Boc Hydroxylamine

Abstract A novel hydroxylamine‐derived aminating agent, O ‐(2‐pyrimidinyl)‐ N ‐Boc hydroxylamine (PymONHBoc), has been designed and synthesized, from readily available 2‐chloropyrimidine. This reagent demonstrates superior shelf stability and ease of handling compared to other hydroxylamine‐derived reagents. Here, we present a metal‐free method for the direct conversion of ketones and aldehydes into sec‐amides and nitriles using PymONHBoc as the aminating agent. This method efficiently converts a wide range of aliphatic and aromatic carbonyl compounds into the corresponding amides and nitriles with good to excellent yields under ambient conditions. The use of PymONHBoc is advantageous, as it facilitates the in situ generation of the activated oxime intermediate, concomitantly producing a non‐interfering byproduct.