Go tandem! The first example of the direct amidation of alcohols with N‐substituted formamides has been developed. A series of tertiary amides, including the challenging N,N‐dimethyl‐substituted amides, were obtained in moderate to good yields under transition‐metal‐free conditions (see scheme). TBHP=tert‐butyl hydroperoxide.
A general organocatalytic asymmetric dehydrated Mannich reaction of fluoroalkyl hemiaminals with ketones is reported. In this Mannich reaction, previously less explored aryl ketones showed great reactivity. By virtue of this efficient method, a wide range of biologically active β-amino ketones were directly obtained. More importantly, two different intermediates involved in the reaction were detected and identified by (19)F NMR and HRMS analysis. Furthermore, the synthetic utility of the products was demonstrated by the synthesis of the biologically active fluoroalkyl β-amino alcohols.
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