5-Alkenylthiazoles as In-Out Dienes in Polar [4 + 2] Cycloaddition Reactions. -The thiazoles (IV) undergo regio-, stereo-, and site-selective Diels-Alder reaction with electron-poor dienophiles to afford various polycyclic thiazole derivatives. With naphthoquinone and DMAD completely oxidized cycloadducts are directly obtained. A mechanism placed at the boundary between a concerted and stepwise process is proposed. -(ALAJARIN*, M.; CABRERA, J.; SANCHEZ-ANDRADA, P.; BAUTISTA, D.; PASTOR, A.; Eur. J. Org. Chem. 2013, 33, 7500-7511, http://dx.