Synthetic Approaches to N‐Methoxy‐N‐methylamides

N ‐Methoxy‐ N ‐methylamides were prepared by the acylation of acid halides, acyl cyanides, esters, lactones, activated amides, and mesyl carboxylates with N , O ‐dimethylhydroxylamine hydrochloride. The reaction of carboxylic acids with alkyl chloroformates, phosphonate reagents, or coupling agents afforded the activated esters, which were converted to N ‐methoxy‐ N ‐methylamides by (CH 3 O)NHCH 3 . N ‐Methoxy‐ N ‐methylamides were also prepared by the oxidative amidation of benzyl alcohols and palladium‐catalyzed aminocarbonylation of organoboronic acids or aryl halides with (CH 3 O)NHCH 3 under CO equivalents. Furthermore, N ‐methoxy‐ N ‐methylamides were produced by the selective substitution of N , O ‐dimethylcarbamoylation agents with organometallic reagents.