Conversion of Organic Amines Into Organic Iodides and Simple Arenes via Metal‐Free Direct Deamination Approach

We present a unified and operationally straightforward strategy for the direct synthesis of iodoarenes, iodoalkanes, and arene derivatives under nitrite‐free conditions. This dual catalytic platform encompasses two mechanistically distinct pathways: (i) a potassium iodide‐catalyzed deamination protocol involving the in situ generation of nitrous acid from hydroxylamine hydrochloride and tert ‐butyl hydroperoxide (TBHP), mediated by iodine (I 2 ), which facilitates diazotization of primary amines followed by C─X bond formation to furnish iodoarenes and iodoalkanes; and (ii) a silane‐mediated deamination pathway that bypasses conventional diazonium intermediates, enabling reductive deamination to access arenes. Both approaches eliminate the need for traditional nitrite salts, offering a metal‐efficient and environmentally benign alternative. The methodology demonstrates broad substrate scope across aromatic and aliphatic amines, affording structurally diverse deaminated products in yields of up to 95%. By avoiding reliance on hazardous nitrite‐based reagents, this work provides a sustainable and versatile platform for the synthesis of valuable iodoarene, iodoalkane, and arene scaffolds with wide synthetic applicability.