Herein, a method for the primary electrophilic amination of primary, secondary, and tertiary organometallic substrates from a bench-stable NH-oxaziridine reagent is described. This work, inspired by our previous studies on the primary amination of arylmetals, expands the applicability of using the di-tert-butyl oxaziridine as an electrophilic source of nitrogen. This facile and highly chemoselective transformation occurs at ambient temperature, without the use of transition metal catalysts, and the products are obtained without purification by column chromatography. The substrate scope includes the formation of 20 aliphatic amines with a diverse functional group tolerance including nitriles, electron-withdrawing trifluoromethyl gropups, thioethers, and fully saturated aliphatic compounds. Interestingly, the transformation was successful for both alkyl magnesium (Grignard) and alkyl zinc carbon-centered nucleophiles. Computational studies were conducted to evaulate the mechanism of N-transfer. Additionally, computational calculations invetigated the basicity of the alkymetals and the differences in reactivity between the Grignard and zinc nucleophiles.

Direct primary electrophilic amination of alkylmetals with NH-oxaziridine

2019 Spring National Meeting

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