Ketenimines as Aza-Dienophiles

<i>N</i>-Aryl ketenimines have been established as highly reactive aza-dienophiles. Intermolecular cycloadditions are achieved upon heating in the presence of 2,5-bis(silyloxy)furans and proceed with high levels of peri-, regio-, chemo- and diastereo-selectivity. Spontaneous C-O cleavage yields oxygenated pyridone derivatives in a highly convergent and redox-neutral manner. Combined experimental and computational studies demonstrate <i>N</i>-aryl ketenimines to be significantly more reactive than imino dienophiles, as a consequence of less distorted transition states. Derivatization studies include the development of isocyanate and cyclic ketenimine equivalents as aza-dienophiles, while extension to a one-pot aza-Diels-Alder/oxa-Diels-Alder sequence provides a three-component approach to complex fused pyridone/pyran systems.