and Stereoselective Diels-Alder Reaction of Ambident Dienophilic Monothiomaleimide.-Both the C=S and C=C functionalities of the N-arylmonothiomaleimides ( I) undergo a (4 + 2) cycloaddition reaction with variously substituted 1,3-butadienes. The C=S group is generally more reactive than the C=C group, especially toward dienes bearing conjugation and electron-attracting groups providing products with complete regioselectivity and with high stereoselectivity. The C=C groups display a high stereoselectivity but a low regioselectivity. Compared with (Ia) the maleimide (Ib) is more reactive and displays a higher C= S vs. C=C chemoselectivity in favor of C=S, while the derivatives (Ic) display quite the reverse reactivity and selectivity. The imide (II) serves as a C=S specific dienophile and reacts with dienes such as ( III) to give only the products (IV). Both hard and soft Lewis acids enhance the reaction rate and increase chemoselectivity in favor of C= S. The outcome of the reactions is rationalized by transition structure analysis based on AM1 calculations. -(TAMARU, Y.; HARAYAMA, H.; SAKATA, H.; KONISHI, H.; FUGAMI, K.; KIMURA, M.; TANAKA, S.; OKAJIMA, T.; FUKAZAWA, Y.; Liebigs Ann./Recl. (1997) 5, 907-923; Dep. Appl. Chem., Fac. Eng., Nagasaki Univ., Bunkyo, Nagasaki 852, Japan; EN)