Transamidation of secondary amides with various amines is demonstrated using tert-butyl nitrite. The reaction proceeds through the N-nitrosamide intermediate and provides the desired products in excellent yields.

A conversion of o-phenylenediamines into benzotriazoles was achieved at room temperature using tert-butyl nitrite. The optimized conditions are also well suited for the transformation of sulfonyl and acyl hydrazines into corresponding azides. This protocol does not require any catalyst or acidic medium. The desired products were obtained in excellent yields in a short span of time.

Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)−N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)−N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.

A practical method is disclosed for the reduction of activated primary and secondary amides into aldehydes using diisobutylaluminum hydride (DIBAL-H) in toluene. A wide range of aryl and alkyl N-Boc,...

A wide range of aryl and alkyl N-Cbz amides were prepared from secondary amides and benzyl chloroformate in the presence of LiHMDS. Application of N-Cbz amides in transamidation was demonstrated with different amines at room temperature in the presence of DBU. The reactivity of N-Cbz amides is comparable with N-Boc and N-Ts amides in transamidation and transesterification reactions. The optimized condition was well-suited for the transesterification reactions with thiols and alcohols. Broad substrate scope and excellent yields are the merits of the developed methodology.