Ac opper-catalyzed electrophilic amidation of aryltrifluoroboratesw ith use of N-methoxyamides is reported. The reactions hows high functional group compatibility derived from two distinct features:1 )the high stability of the N-methoxyamides and 2) the nonbasic mild conditions in the presence of LiCl. The developed method can also be applied to the synthesis of enamides, which are widely distrib-uted in natural products. Preliminary mechanistic studies suggest that the initial step is the transmetalation of the aryltrifluoroborate by the assistanceo fL iCl, and the resulting aryl copper intermediate provides the anilidet hrough non-S N 2o xidative additiont ot he N-methoxyamidea nd subsequentr eductiveelimination.Scheme1.Copper-mediated and copper-catalyzed electrophilic amidation of organoboron reagents.

A copper-catalyzed electrophilic enamidation starting from alkynes is reported. Hydrozirconation of an alkyne with the Schwartz reagent forms a vinyl zirconium intermediate, which directly undergoes a copper-catalyzed electrophilic enamidation with dioxazolones. High functional group tolerance of hydrozirconation enables the use of functionalized alkynes including esters. The developed conditions are successfully applied to syntheses of partial structures found in biologically active natural products.