Synthesis of Cyclic N -Acyl Amidines by [3 + 2] Cycloaddition of N -Silyl Enamines and Activated Acyl Azides.

In this study, we describe the synthesis of cyclic N -acyl amidines from readily available N -heteroarenes. The synthetic methodology utilized the versatile N -silyl enamine intermediates from the hydrosilylation of N -heteroarenes for the [3 + 2] cycloaddition reaction step. We evaluated various acyl azides and selected an electronically activated acyl azide, thereby achieving a reasonable yield of cyclic N -acyl amidines. We analyzed the relationship between the reactivity of each step and the electronic nature of substrates using in situ nuclear magnetic resonance spectroscopy. In addition, we demonstrated gram-scale synthesis using the proposed methodology.