An Efficient Protocol for the Synthesis of Primary Amides via Rh‐Catalyzed Rearrangement of Aldoximes

Abstract

A system consisting of catalytic amounts of [Rh(CH 2 = CH 2 )Cl] 2 / PPh 2 Cy, and PhCl as the solvent efficiently catalyzes selective rearrangement of aldoximes to furnish various primary amides in moderate to good yields. Replacing the [Rh(CH 2 = CH 2 )Cl] 2 with Rh(NBD) 2 OTf enables the superior transformation to afford the amides with up to 99% yields. Attractive synthetic features associated with this methodology include absence of cocatalysts, broad functional group tolerance, good to excellent yields, low metal loadings, and operational convenience.[a] Dr.

Mechanochemical Synthesis of Primary Amides

“…The resulting solid was washed with petroleum ether (2 × 2.5 mL) to afford the pure amides. The compounds thus obtained, including 2a – 2c , 27 2d , 2g and 2r , 23a 2e , 28 2f , 29 2h and 2j , 30 2i , 31 2k , 32 2l , 33 and 6 ( 34 ) showed characterization data coincident with those found in the literature, and copies of their NMR spectra can be found in the Supporting Information .…”

Transamidation for the Synthesis of Primary Amides at Room Temperature

“…To address these issues, more practical and efficient methods have been developed. For example, the employment of activators for the conversion of carboxylic acids into amides, metal-catalyzed hydration of nitriles, the rearrangement of aldoximes, Pd-catalyzed aminocarbonylation of aryl halides, C–C bond cleavage of ethylarenes, decarboxylative ammoxidation of phenylacetic acid, oxidation of primary benzyl amines, and oxidative amidation of aldehydes, benzyl alcohols, methyl ketone, or methylarenes . However, there are no reports that secondary or tertiary amides have been employed as a starting material toward the synthesis of primary amides with the exception of those using a deprotection process.…”