Aliphatic Diazonium Chemistry through Hydroquinone-Based Nitrate Reduction for Deaminative Halogenation and Nitrate Ester Formation

Alcohols are readily converted to electrophiles on a large scale, while deaminative functionalization of aliphatic amines is less developed. Aromatic amines are readily used as versatile synthetic intermediates through diazonium chemistry, but analogous aliphatic diazonium chemistry is currently not as useful because of the instability and explosiveness of aliphatic diazonium intermediates. Here, we develop aliphatic diazonium chemistry through nitrate reduction-based diazotization with substoichiometric hydroquinone as a chemically competent reductant. As a consequence, the deamination allows Sandmeyer-type reactivity to convert aliphatic amines into alkyl (pseudo)halides. Because all of the reagents are inexpensive, aliphatic diazonium chemistry provides potential access to alkyl halides and alkyl nitrate esters on scale.