Alkylamines are ubiquitous intermediates and reagents used in fine chemicals industry and their selective late-stage modification and functionalization are the important synthetic transformations. In this work we present two new protocols for oxidative acyldealkylation of tertiary amines that utilize either metal-free or Pd-catalyzed systems with O2 as oxidant and carboxylic acid anhydrides (RCO)2O as the acylating agents. The reactions are operational in the temperature range of 20 – 100 oC. A variety of N,N-dialkylanilines and trialkylamines were selectively transformed to the corresponding tertiary acylamides in modest to excellent yields. When methylamines are used, the corresponding formamides are formed as the byproducts. The reactivity of the alkyl groups that are removed decreases in the order Me &gt; Et, n-Bu &gt;&gt; i-Pr, whereas the aryl groups, if present, remain intact. We use mechanistic tests and DFT calculations to analyze plausible mechanisms of the reactions studied.

Selective metal-free and Pd-catalyzed aerobic acyldealkylation of tertiary amines

ACS Spring Meeting 2021

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